Shikimic acid- or 3-dehydroshikimic acid-derived esters or amides or sulfated or sulfonated derivatives thereof for use as surfactants

Abstract

The present invention relates to the use of shikimic acid- or 3-dehydroshikimic acid-derived esters or amides or sulfated or sulfonated derivatives thereof or stereoisomers or stereoisomer mixtures thereof as surfactants, to surfactant compositions comprising such compounds, to specific shikimic acid- or 3-dehydroshikimic acid-derived esters or amides or sulfated or sulfonated derivatives thereof or stereoisomers or stereoisomer mixtures thereof and to methods for preparing such compounds.

Description

[0001] Shikimic acid- or 3-dehydroshikimic acid-derived esters or amides or sulfated or sulfonated derivatives thereof for use as surfactants

[0002] The present invention relates to the use of shikimic acid- or 3-dehydroshikimic acid- derived esters or amides or sulfated or sulfonated derivatives thereof or stereoisomers or stereoisomer mixtures thereof as surfactants, to surfactant compositions comprising such compounds, to specific shikimic acid- or 3-dehydroshikimic acid-derived esters or amides or sulfated or sulfonated derivatives thereof or stereoisomers or stereoisomer mixtures thereof and to methods for preparing such compounds.

[0003] TECHNICAL BACKGROUND

[0004] Surfactants are compounds which lower the surface tension between two phases, in particular between two liquids. Surfactants generally are organic amphiphilic compounds, i.e. , compounds comprising both hydrophobic (= lipophilic) and hydrophilic groups. Such compounds find use, e.g., as detergents, wetting agents, foaming agents, emulsifiers, and dispersants.

[0005] Being commodities, surfactants are produced on a large scale and used universally on industrial / institutional as well as on private level. After use, residual surfactants are generally discharged into sewage systems or directly into surface waters, and most of them end up dispersed in different environmental compartments such as soil, water or sediment, at least if the wastewater has not undergone a secondary treatment in wastewater treatment plants. The problems related with surfactants, especially with those not derived from natural sources, such as toxic effects on various aquatic and other organisms, are well known.

[0006] Furthermore, one of the presently most pressing needs worldwide is the reduction of the carbon footprint of all sorts of products, processes and activities.

[0007] Currently, most surfactants, such as linear alkylbenzene sulfonates (LAS), sulfosuccinates, alcohol alkoxylates or alcohol alkoxylate sulfates are produced starting exclusively or at least predominantly from petrochemical starting materials, i.e. from material gained from fossil carbon sources.

[0008] It was the object of the present invention to provide compounds which are suitable as surfactants. Advantageously they should have a reduced carbon footprint, especially by being at least partially available from renewable sources, or should be readily biodegradable, or ideally both available from renewable sources and readily biodegradable. These objects are achieved by the compounds of the formulae (I. a) or (l.b) depicted below. The compounds can be prepared from gallic acid, shikimic acid or 3-dehydroshi- kimic acid, which in turn are obtainable from renewable sources. Also the radical Y can be derived from alcohols or amines obtainable from renewable sources.

[0009] Esters and amides of shikimic acid or 3-dehydroshikimic acid have been described for various purposes. CN 116120180 A describes the use of n-dodecylshikimate as restorative agent or repairing agent for damaged hair. The mono-n-tridecylamide of shikimic acid is mentioned for a similar purpose. WO 2024 / 086307 mentions the use of octyl shikimate as absorption enhancer (in the sense of increasing the gastrointestinal absorption of food components). WO 98 / 03169 describes the use of certain alkyl 3-dehy- droshikimates as antioxidants. CN 101973874 describes the preparation of certain alkyl 3-dehydroshikimates from the corresponding shikimates and mentions, too, that 3-de- hydroshikimates have an antioxidant activity. WO 2021 / 252290 mentions N-hexa- decylshikimic acid amide as NKT-2-activator.

[0010] SUMMARY OF THE INVENTION

[0011] The invention relates to the use of a compound of the formula (I. a) or (l.b) where

[0012] R1ais a group -OR1aaor an oxo group (=0);

[0013] R1bis a group -OR1bbor an oxo group (=0);

[0014] R1aa, R2a, R3a, R1bb, R2band R3b, independently of each other, are hydrogen or a group -S(O)3H or -S(O)3'M+, where M+is a metal cation equivalent or an ammonium cation;

[0015] R4and R5are hydrogen or one of R4and R5is a group -S(O)3H or -S(O)3'M+, where M+is a metal cation equivalent or an ammonium cation; and the other is hydrogen; and

[0016] Y is a group -OR6or -NR7R8, where R6is Ce-Cso-alkyl or Ce-Cso-alkenyl;

[0017] R7is Ce-Cso-alkyl or Ce-Cso-alkenyl; and

[0018] R8is hydrogen, Ci-Cso-alkyl or Cs-Cso-alkenyl; or of a mixture of different compounds (I. a) and / or (l.b), or of a stereoisomer of the compound (I. a) or (l.b), or of a mixture of different stereoisomers of the compounds (I. a) and / or (l.b) as a surfactant.

[0019] In a specific embodiment, the compound (I. a) is not a compound wherein R4and R5are hydrogen and simultaneously R1bis a group -OR1bb.

[0020] The invention relates also to a surfactant composition comprising a compound of the formula (I. a) or (l.b) as defined above or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b), and at least one component selected from the group consisting of: water, organic solvents, surfactants different from the compounds (I. a) and (l.b), fragrances, antimicrobial agents, sequestrants, enzymes, enzyme stabilizers, hydrotropic agents, bleaching agents, dyes, pigments, pH adjusting agents, pearlescents, opacifiers, viscosity modifiers, and inorganic salts.

[0021] The invention relates moreover to a a compound of the formula (I. a) or (l.b) as defined above or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b), except for the following compounds:

[0022] - compounds (l.b) wherein R1ais OH or oxo, R2aand R3aare hydrogen, Y is -OR6and R6is dodecyl;

[0023] - compound (l.b) wherein R1ais oxo, R2aand R3aare hydrogen, Y is OR6and R6is n- hexyl;

[0024] - compound (l.b) wherein R1ais OH, R2aand R3aare hydrogen, Y is -NR7R8, R7is n- hexadecyl and R8is hydrogen.

[0025] Furthermore, the invention relates to a method for preparing a compound of the formula (I. a) as defined above, wherein one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other of R4and R5is hydrogen, comprising

[0026] (i.1) reacting a compound (II) where Y is as defined above and R1ais oxo or OR1aa, where R1aais hydrogen, with a sulfonation agent; and

[0027] (ii.1) if desired reacting the compound (I. a) obtained in step (i.1) with a base to obtain a compound (I. a) wherein one of R4and R5is a group -S(O)3'M+and the other of R4and R5is hydrogen, and where optionally also one of R1aa(if present) R2aand R3ais a group -S(O)3'M+; and to a method for preparing a compound of the formula (I. a) as defined above, wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3aa group -S(O)3H or -S(O)3'M+, comprising

[0028] (i.2) reacting a compound (III) where Y is as defined above and R1ais oxo or OR1aa, where R1aais hydrogen, with a sulfonation agent to obtain a compound (I. a) wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3ais a group -S(O)3H; and

[0029] (ii.2) if desired reacting the compound (I. a) obtained in step (i.2) with a base to obtain a compound (I. a) wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3ais a group -S(O)3'M+.

[0030] The invention also relates to a method for cleaning or washing a surface or a material, comprising bringing the surface or material into contact with a compound (I. a) or (l.b) or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b); or with a composition containing a compound (I. a) or (l.b) or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b), e.g. with the above-mentioned surfactant composition.

[0031] DETAILED DESCRIPTION OF THE INVENTION

[0032] Definitions:

[0033] If in the formula (I. a), R1ais an oxo group (=0), this means more precisely expressed that R1a, together with the geminally bound hydrogen atom, forms an oxo group =0. In other words, the moiety CHR1aforms in this case a carbonyl group C=O.

[0034] Analogously, if in the formula (l.b), R1bis an oxo group (=0), this means more precisely expressed that R1b, together with the geminally bound hydrogen atom, forms an oxo group =0. In other words, the moiety CHR1bforms in this case a carbonyl group C=0.

[0035] The term “alkyl” is used in the usual sense and stands for saturated straight-chain or branched aliphatic non-cyclic hydrocarbon radicals. Cn-Cm-alkyl has n to m carbon atoms. "Ci-Cao-Alkyl" is a saturated aliphatic non-cyclic hydrocarbon radical having 1 to 30 carbon atoms. "Ce-Cso-alkyl" is a saturated straight-chain or branched aliphatic non- cyclic hydrocarbon radical having 6 to 30 carbon atoms. "Cs-Cso-alkyl" is a saturated straight-chain or branched aliphatic non-cyclic hydrocarbon radical having 8 to 30 carbon atoms. "C -Ci8-alkyl" is a saturated straight-chain or branched aliphatic non-cyclic hydrocarbon radical having 10 to 18 carbon atoms. "C -Ci4-alkyl" is a saturated straight-chain or branched aliphatic non-cyclic hydrocarbon radical having 10 to 14 carbon atoms. Examples for C -Ci4-alkyl are n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n- tetradecyl and structural isomers thereof. Examples for C -Cis-alkyl are, in addition to those mentioned for Cw-C -alkyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octade- cyl and structural isomers thereof. Examples for Cs-Cso-alkyl are, in addition to those mentioned for C -Cis-alkyl, n-octyl, n-nonyl, n-nonadecyl, n-eicosyl, n-henicosyl, n-do- cosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-octacosyl, n-nonacosyl, n- triacontyl and structural isomers thereof. Examples for Ce-Cso-alkyl are, in addition to those mentioned for Cs-Cso-alkyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpen- tyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dime- thylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trime- thylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-hep- tyl and (other) structural isomers thereof. Examples for Ci-Cso-alkyl are, in addition to those mentioned for Ce-Cso-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dime- thylpropyl, 1-ethylpropyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl and other structuryl isomers thereof.

[0036] Strictly speaking, the term "alkenyl" indicates monounsaturated (i.e. containing one C- C double bond) straight-chain or branched aliphatic non-cyclic hydrocarbon radicals. In terms of the present invention, the term "alkenyl" however also encompasses polyunsaturated straight-chain or branched aliphatic non-cyclic hydrocarbon radicals having 2 (alkadienyl), 3 (alkatrienyl) or more (alkapolyenyl) C-C double bonds. Examples for C2- Cso-alkenyl in the strict sense (just one C-C double bond) are ethenyl, 1-propenyl, 2- propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-me- thyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3- pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1- methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-

[0037] 3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2-propenyl, 1 ,2-dimethyl-1-propenyl, 1 ,2- dimethyl-2-propenyl, 1 -ethyl- 1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3- hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1- pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2- pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3- pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4- pentenyl, 4-methyl-4-pentenyl, 1 ,1-dimethyl-2-butenyl, 1 ,1-dimethyl-3-butenyl, 1 ,2-di- methyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1-bu- tenyl, 1,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dime- thyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-

[0038] 1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1-ethyl-1-me- thyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-heptenyl,

[0039] 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, 1-octenyl, 2-octenyl, 3-oc- tenyl, 4-octenyl, 5-octenyl, 6-octenyl, 7-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 4- nonenyl, 5-nonenyl, 6-nonenyl, 7-nonenyl, 8-nonenyl, 1 -decenyl, 2-decenyl, 3-decenyl,

[0040] 4-decenyl, 5-decenyl, 6-decenyl, 7-decenyl, 8-decenyl, 9-decenyl, 1 -undecenyl, 2-un- decenyl, 3-undecenyl, 4-undecenyl, 5-undecenyl, 6-undecenyl, 7-undecenyl, 8-unde- cenyl, 9-undecenyl, 10-undecenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 11-dodecenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- and 12-tridecenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12- and 13-tetradecenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- and 14-pentadecenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14- and 15-hexade- cenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15- and 16-heptadecenyl, 1- , 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16- and 17-octadecenyl, the nonadecenyls, the eicosenyls, the henicosenylss, the docosenylss, the tricosenyls, the tetracosenyls, the pentacosenyls, the hexacosenyls, the heptacosenyls, the octacosenyls, the nonacosenyls, the triacontenyls and the structural isomers thereof. Alkadienyls have at least 4 carbon atoms and 2 C-C double bonds. Examples are buta- 1 ,3-dien-1-yl, buta-1 ,3-dien-2-yl, penta-1 ,3-dien-1-yl, penta-1 ,3-dien-2-yl, penta-1 ,3- dien-3-yl, penta-1 ,3-dien-4-yl, penta-1 ,3-dien-5-yl, penta-1 ,4-dien-1-yl, penta-1 ,4-dien- 2-yl, penta-1 ,4-dien-3-yl, and the higher homologues with up to 30 carbon atoms. Alka- trienyls have at least 6 carbon atoms and 3 C-C double bonds. Examples are 1 ,3,5- hexatrien-1-yl, 1 ,3,5-hexatrien-2-yl, 1 ,3,5-hexatrien-3-yl, 1 ,3,5-heptatrien-1-yl, 1 ,3,5- heptatrien-2-yl, 1 ,3,5-heptatrien-3-yl, 1 ,3,5-heptatrien-4-yl, 1 ,3,5-heptatrien-5-yl, 1 ,3,5- heptatrien-6-yl, 1 ,3,5-heptatrien-7-yl, and the higher homologues with up to 30 carbon atoms.

[0041] Metal cation equivalent stands for (Mm+)i / m, where M stands for the metal and m is its valence. Thus, in case of alkali metals, the metal cation equivalent stands for M+(M being the alkali metals, e.g. Li, Na, K) and thus, for example for Li+, Na+or K+, in case of alkaline earth metals, the metal cation equivalent stands for (M2+)I / 2 (M being the alkaline earth metal, e.g. Mg or Ca) and thus, for example for (Mg2+)i / 2 or (Ca2+)i / 2, and in case of trivalent metal cations, the metal cation equivalent stands for (M3+)I / 3 (M being a metal which can be trivalent, e.g. Al) and thus, for example for (AI3+)I / 3.

[0042] Unless specified otherwise, ammonium cation means ammonium in the proper sense, i.e. a group NH4+.

[0043] The term "stereoisomers" as used in context with the present invention relates specifically to optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one stereogenic center in the molecule, but also to Z / E isomers. The compounds of the formula (I. a) and (l.b) wherein R1aand R1bis oxo have at least three stereogenic centers, namely the carbon atoms carrying -OR2a, -OR3aand the group -C(O)-Y in case of (I. a), and the carbon atoms carrying -OR2b, -OR3band the group -C(O)-Y in case of (l.b). The compounds of the formula (I. a) and (l.b) wherein R1aand R1bare -OR1aaor -OR1bb, respectively, have at least four stereogenic centers, namely the carbon atoms carrying R1a, -OR2a, -OR3aand the group -C(O)-Y in case of (I. a), and the carbon atoms carrying R1b, -OR2b, -OR3band the group -C(O)-Y in case of (l.b). If in compounds (I. a) R5is a group -S(O)3H or -S(O)3'M+, the carbon atom carrying R5is a further stereogenic center. Further stereogenic centers may be present in the radicals R6, R7and R8(in R8only if this is alkyl or alkenyl with 4 or more carbon atoms). If R6, R7and / or R8are alkenyl, depending on the position of the double bond, Z / E isomers might be present.

[0044] In terms of the present invention, the term "pure enantiomer" is understood as a non- racemic mixture of a specific compound, where the desired enantiomer is present in an enantiomeric excess of > 90 %ee. In terms of the present invention, the term "pure diastereomer" is understood as a mixture of the diastereomers of a specific compound, where the desired diastereomer is present in an amount of > 90 %, based on the total amount of diastereomers of said compound.

[0045] In the present context, the term "compound (I. a)" or "compound (l.b)", when not defined as a specific stereoisomer or a specific mixture of stereoisomers, refers to the form of the compound as it is obtained in a method used for its production. The term is however also used if it is not necessary or not possible to specify in more detail the stereochemistry of the compound (I. a) or (l.b). If the compounds are prepared from shikimic acid, the carbon atoms carrying -OR1aa, -OR2aand -OR3aI -OR1bb, -OR2band -OR3bwill have the stereochemistry present in shikimic acid, unless the esterification reaction or amidation reaction (for introducing Y) and / or the sulfonation (for introducing -S(O)3H or -S(O)3'M+groups) leads to (some) racemization. If the compounds are prepared from 3-dehydroshikimic acid, the carbon atoms carrying -OR2aand -OR3aI -OR2band -OR3bwill have the stereochemistry present in 3-dehydroshikimic acid, unless the esterification reaction or amidation reaction (for introducing Y) and / or any hydrogenation reaction (e.g. for reducing the oxo group R1aor R1band / or the C-C double bond in the ring) and / or the sulfonation (for introducing -S(O)3H or -S(O)3'M+groups) leads to (some) racemization.

[0046] In terms of the present invention, the term “sulfonation agent” is used both for a sulfonation agent in the proper sense, i.e. an agent which introduces a sulfonic acid group (-S(=O)2-OH) or a derivative thereof into an organic molecule, where the sulfur atom is bound to a carbon atom, as well as for an sulfation agent, i.e. an agent which (formally) converts an -OH group into a sulfate (= sulfuric ester) group -O-S(=O)2-OH or a derivative thereof. The agent is termed “sulfonation agent” even if a further step (generally hydrolysis) is required to obtain the sulfonic acid, sulfonate or sulfate group.

[0047] The remarks made below concerning preferred definitions of the variables are valid on their own as well as preferably in combination with each other concerning the compounds of formula (I. a) and (l.b), as defined herein, where applicable, as well as concerning the compositions, uses and methods of the invention as defined herein.

[0048] Embodiments (E.x) of the invention

[0049] General and preferred embodiments E.x are summarized in the following, non-exhaus- tive list. Further preferred embodiments become apparent from the paragraphs following this list. E.1. The use of a compound of the formula (I. a) or (l.b) where

[0050] R1ais a group -OR1aaor an oxo group (=0);

[0051] R1bis a group -OR1bbor an oxo group (=0);

[0052] R1aa, R2a, R3a, R1bb, R2band R3b, independently of each other, are hydrogen or a group -S(O)3H or -S(O)3'M+, where M+is a metal cation equivalent or an ammonium cation;

[0053] R4and R5are hydrogen or one of R4and R5is a group -S(O)3H or -S(O)3'M+, where M+is a metal cation equivalent or an ammonium cation; and the other is hydrogen; and

[0054] Y is a group -OR6or NR7R8, where

[0055] R6is Ce-Cso-alkyl or Ce-Cso-alkenyl;

[0056] R7is Ce-Cso-alkyl or Ce-Cso-alkenyl; and

[0057] R8is hydrogen, Ci-Cso-alkyl or Cs-Cso-alkenyl; or of a mixture of different compounds (I. a) and / or (l.b), or of a stereoisomer of the compound (I. a) or (l.b), or of a mixture of different stereoisomers of the compounds (I. a) and / or (l.b) as a surfactant.

[0058] E.2. The use according to embodiment E.1 , where in compounds (I. a)

[0059] R1ais a group -OR1aaor an oxo group (=0); and

[0060] R1aa, R2a, R3a, R4and R5are hydrogen; or one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen; and R1aa, R2aand R3a, independently of each other, are hydrogen or a group -S(O)3H or -S(O)3'M+; where preferably one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen. E.3. The use according to embodiment E.1 , where in compounds (I. a)

[0061] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0062] R1ais oxo and at least one of R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3'M+; or R1ais OR1aaand at least one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3-M.

[0063] E.4. The use according to embodiment E.3, where in compounds (I. a)

[0064] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0065] R1ais oxo, one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen, and R2aand R3aare independently hydrogen or a group -S(O)3H or -S(O)3'M+; or

[0066] R1ais OR1aa, one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen, and R1aa, R2aand R3aare independently hydrogen or a group -S(O)3H or -S(O)3-M+.

[0067] E.5. The use according to embodiment E.3, where in compounds (I. a)

[0068] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0069] R1ais oxo and on average one of R2a, R3a, R4and R5is a group -S(O)3H or -S(0)3'M+, preferably -S(0)3'M+; and the other three of R2a, R3a, R4and R5are hydrogen, or

[0070] R1ais 0R1aaand on average one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(0)3'M+, preferably -S(0)3'M+; and the other four of R1aa,R2a, R3a, R4and R5are hydrogen.

[0071] E.6. The use according to embodiment E.4 or E.5, where in compounds (I. a)

[0072] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0073] R1ais oxo, one of R4and R5(preferably R5) is a group -S(O)3H or -S(0)3'M+and the other (preferably R4) is hydrogen, and R2aand R3aare hydrogen, or R1ais 0R1aa, one of R4and R5is a group -S(O)3H or -S(0)3'M+and the other is hydrogen, and R1aa, R2aand R3aare hydrogen.

[0074] E.7. The use according to embodiment E.1 , where in compounds (I. a) one of R4and R5(preferably R5) is -S(O)3H or -S(0)3'M+, and the other of R4and R5(preferably R4) is hydrogen.

[0075] E.8. The use according to embodiment E.7, where in compounds (I. a) one of R4and R5(preferably R5) is -S(0)3'M+, and the other of R4and R5(preferably R4) is hydrogen.

[0076] E.9. The use according to any of the preceding embodiments, where in compounds (I. a) one of R4and R5(preferably R5) is -S(0)3'M+and the other of R4and R5(preferably R4) is hydrogen; R2aand R3aare hydrogen; and R1ais oxo or 0R1aa, wherein R1aais hydrogen.

[0077] E.10. The use according to embodiment E.9, where R1ais 0R1aa, wherein R1aais hydrogen. E.11. The use according to any of the preceding embodiments, where in compounds (I. a) R1ais OR1aa.

[0078] E.12. The use according to any of the preceding embodiments, where in compounds (l.b)

[0079] R1bis oxo and R2band R3bare hydrogen; or

[0080] R1bis OH and R2band R3bare hydrogen.

[0081] E.13. The use according to embodiment E.12, where R1bis OH and R2band R3bare hydrogen.

[0082] E.14. The use according to any of the preceding embodiments, where the compound of the formula (I. a) is a compound of the formula (I .a.1 ), (I. a.2) or (I. a.3), and the compound of the formula (l.b) is a compound of the formula (l.b.1), (l.b.2) or (l.b.3)

[0083] E.15. The use according to any of the preceding embodiments, where M+is an alkali metal cation or an alkaline earth metal cation equivalent.

[0084] E.16. The use according to embodiment E.15, where M+is Na+, K+, (Mg2+)i / 2 or (Ca2+)i / 2.

[0085] E.17. The use according to embodiment E.16, where M+is Na+or K+.

[0086] E.18. The use according to embodiment E.17, where M+is Na+.

[0087] E.19. The use according to any of the preceding embodiments, where R6and R7, independently of each other, are Cs-Cso-alkyl.

[0088] E.20. The use according to embodiment E.19, where R6and R7, independently of each other, are Cio-Ci8-alkyl. E.21. The use according to embodiment E.20, where R6and R7, independently of each other, are linear C -Cis-alkyl.

[0089] E.22. The use according to embodiment E.20, where R6and R7, independently of each other, are C -C -alkyl.

[0090] E.23. The use according to embodiment E.22, where R6and R7, independently of each other, are linear Cw-C -alkyl.

[0091] E.24. The use according to embodiment E.21 , where R6and R7, independently of each other, are n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

[0092] E.25. The use according to embodiment E.24, where R6and R7are n-dodecyl.

[0093] E.26. The use according to any of the preceding embodiments, where R8is hydrogen.

[0094] E.27. The use according to any of the preceding embodiments, where Y is -OR6.

[0095] E.28. The use according to any of the preceding embodiments, of a compound (I. a), wherein one of R4and R5(preferably R5) is -S(O)3H or -S(O)3'M+, and the other of R4and R5(preferably R4) is hydrogen; R2aand R3aare hydrogen; R1ais oxo or OR1aa, wherein R1aais hydrogen; Y is OR6and R6is Cw-C -alkyl.

[0096] E.29. The use according to embodiment E.28, of a compound (I. a), wherein one of R4and R5(preferably R5) is -S(O)3'M+, and the other of R4and R5(preferably R4) is hydrogen; R2aand R3aare hydrogen; R1ais oxo or OR1aa, wherein R1aais hydrogen; Y is OR6and R6is Cw-C -alkyl.

[0097] E.30. The use according to embodiment E.29, of a compound (I. a), wherein one of R4and R5(preferably R5) is -S(O)3'M+, where M+is an alkali metal cation; and the other of R4and R5(preferably R4) is hydrogen; R2aand R3aare hydrogen; R1ais OR1aa, wherein R1aais hydrogen; Y is OR6and R6is C -C -alkyl.

[0098] E.31. The use according to any of the preceding embodiments, of a compound (l.b), wherein R1bis OH, R2band R3bare hydrogen, Y is OR6and R6is C -C -alkyl.

[0099] E.32. The use according to any of the preceding embodiments, where at least a part of the compounds (I. a) and (l.b) is derived from gallic acid, shikimic acid or 3-dehy- droshikimic acid which is obtained from a renewable source and / or is derived from an alkanol R6OH or an amine NHR7R8which is obtained from a renewable source.

[0100] E.33. The use according to embodiment E.32, where in the compounds (I. a) and (l.b) at least 20 mol-% of the carbon atoms, relative to the total amount of carbon atoms in the compounds (I. a) and (l.b), stem from a renewable source.

[0101] E.34. The use according to embodiment E.33, where in the compounds (I. a) and (l.b) at least 20 mol-% of the carbon atoms, relative to the total amount of carbon atoms in the compounds (I. a) and (l.b), are bio-based.

[0102] E.35. The use according to any of the preceding embodiments, in homecare compositions, l&l cleaning compositions, personal care compositions or pesticide adjuvant compositions.

[0103] E.36. The use according to any of the preceding embodiments, for stabilizing oil-in-wa- ter emulsions or aqueous dispersions. E.37. A surfactant composition comprising a compound of the formula (I. a) or (l.b) as defined in any of embodiments E.1 to E.34 or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b), and at least one component selected from the group consisting of: water, organic solvents, surfactants different from the compounds (I. a) and (l.b), fragrances, antimicrobial agents, se- questrants, enzymes, enzyme stabilizers, hydrotropic agents, bleaching agents, dyes, pigments, pH adjusting agents, pearlescents, opacifiers, viscosity modifiers, and inorganic salts.

[0104] E.38. The surfactant composition according to embodiment E.37, which is selected from the group consisting of homecare compositions, l&l cleaning compositions, personal care compositions and pesticide adjuvant compositions.

[0105] E.39. The surfactant composition according to any of embodiments E.37 or E.38, where the compound of the formula (l.b) is none of the compounds selected from the group consisting of C6-Ci2-alkylesters of shikimic acid, C6-Ci2-alkylesters of 3- dehydroshikimic acid, N-hexadecyl shikimic acid amide and N-tridecyl shikimic acid amide.

[0106] E.40. The surfactant composition according to any of embodiments E.37 to E.39, where in compounds of the formula (l.b) at least one of R1bb, R2band R3bis a group -S(O)3H or -S(O)3'M+.

[0107] E.41. A compound of the formula (I. a) or of the formula (l.b) or a stereoisomer of the compound (I. a) or (l.b) as defined in any of embodiments E.1 to E.34; except for following compounds: compounds (l.b) wherein R1ais OH or oxo, R2aand R3aare hydrogen, Y is OR6and R6is dodecyl; compound (l.b) wherein R1ais oxo, R2aand R3aare hydrogen, Y is OR6and R6is n- hexyl; compound (l.b) wherein R1ais OH, R2aand R3aare hydrogen, Y is NR7R8, R7is n- hexadecyl and R8is hydrogen.

[0108] E.42. The compound according to embodiment E.41 , where the compound of the formula (l.b) is none of the compounds selected from the group consisting of C6-C12- alkylesters of shikimic acid, C6-Ci2-alkylesters of 3-dehydroshikimic acid, N-hexa- decyl shikimic acid amide and N-tridecyl shikimic acid amide.

[0109] E.43. The compound according to any of embodiments E.41 or E.42, where in compounds of the formula (l.b) at least one of R1bb, R2band R3bis a group -S(O)3H or -S(O)3-M+.

[0110] E.44. The compound according to embodiment E.41 , where in compounds (I. a) R1ais a group -OR1aaor an oxo group (=0); and R1aa, R2a, R3a, R4and R5are hydrogen; or one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen; and R1aa, R2aand R3a, independently of each other, are hydrogen or a group -S(O)3H or -S(O)3'M+; where preferably one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen.

[0111] E.45. The compound according to embodiment E.44, where one of R4and R5(preferably R5) is a group -S(O)3H or -S(O)3'M+and the other (preferably R4) is hydrogen.

[0112] E.46. The compound according to embodiment E.44, where in compounds (I. a)

[0113] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0114] R1ais oxo and at least one of R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3'M+; or R1ais OR1aaand at least one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3-M.

[0115] E.47. The compound according to embodiment E.46, where in compounds (I. a)

[0116] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0117] R1ais oxo, one of R4and R5(preferably R5) is a group -S(O)3H or -S(O)3'M+and the other (preferably R4) is hydrogen, and R2aand R3aare independently hydrogen or a group -S(O)3H or -S(O)3'M+; or

[0118] R1ais OR1aa, one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen, and R1aa, R2aand R3aare independently hydrogen or a group -S(O)3H or -S(0)3-M+.

[0119] E.48. The compound according to embodiment E.46, where in compounds (I. a)

[0120] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0121] R1ais oxo and on average one of R2a, R3a, R4and R5is a group -S(O)3H or -S(0)3'M+, preferably -S(0)3'M+; and the other three of R2a, R3a, R4and R5are hydrogen, or

[0122] R1ais 0R1aaand on average one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(0)3'M+, preferably -S(0)3'M+; and the other four of R1aa,R2a, R3a, R4and R5are hydrogen.

[0123] E.49. The compound according to embodiment E.47 or E.48, where in compounds (I. a) R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0124] R1ais oxo, one of R4and R5(preferably R5) is a group -S(O)3H or -S(0)3'M+and the other (preferably R4) is hydrogen, and R2aand R3aare hydrogen, or R1ais 0R1aa, one of R4and R5is a group -S(O)3H or -S(0)3'M+and the other is hydrogen, and R1aa, R2aand R3aare hydrogen.

[0125] E.50. The compound according to any of embodiments E.41 to E.49, where in compounds (I. a) one of R4and R5(preferably R5) is -S(0)3'M+and the other of R4and R5(preferably R4) is hydrogen; R2aand R3aare hydrogen; and R1ais oxo or 0R1aa, wherein R1aais hydrogen. E.51. The compound according to embodiment E.50, where R1ais OR1aa, wherein R1aais hydrogen.

[0126] E.52. The compound according to any of the embodiments E.41 to E.51 , where in compounds (I. a) R1ais OR1aa.

[0127] E.53. The compound according to any embodiments E.41 to E.42, where in compounds (l.b)

[0128] R1bis oxo and R2band R3bare hydrogen; or

[0129] R1bis OH and R2band R3bare hydrogen.

[0130] E.54. The compound according to embodiment E.53, where R1bis OH and R2band R3bare hydrogen.

[0131] E.55. The compound according to any of embodiments E.41 to E.54, where the compound of the formula (I. a) is a compound of the formula (l.a.1), (I. a.2) or (I. a.3), and the compound of the formula (l.b) is a compound of the formula (l.b.1), (l.b.2) or (l.b.3)

[0132] (l.b.1) (l b.2) (l-b.3)

[0133] E.56. The compound according to any of embodiments E.41 to E.55, where M+is an alkali metal cation or alkaline earth metal cation equivalent.

[0134] E.57. The compound according to embodiment E.56, where M+is Na+, K+, (Mg2+)i / 2 or (Ca2+)i / 2.

[0135] E.58. The compound according to embodiment E.57, where M+is Na+or K+.

[0136] E.59. The compound according to embodiment E.58, where M+is Na+.

[0137] E.60. The compound according to any of embodiments E.33 to E.48, where R6and R7, independently of each other, are Cs-Cso-alkyl. E.61. The compound according to embodiment E.60, where R6and R7, independently of each other, are C -Cis-alkyl.

[0138] E.62. The compound according to embodiment E.61 , where R6and R7, independently of each other, are linear Cio-Ci8-alkyl.

[0139] E.63. The compound according to embodiment E.61 , where R6and R7, independently of each other, are C -C -alkyl.

[0140] E.64. The compound according to embodiment E.63, where R6and R7, independently of each other, are linear Cw-C -alkyl. specifically n-dodecyl.

[0141] E.65. The compound according to embodiment E.62, where R5and R6, independently of each other, are n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

[0142] E.66. The compound according to embodiment E.65, where R6and R7are n-dodecyl.

[0143] E.67. The compound according to any of embodiments E.41 to E.66, where R8is hydrogen.

[0144] E.68. The compound according to any of embodiments E.41 to E.67, where Y is -OR6.

[0145] E.69. The compound according to any of embodiments E.41 to E.68, where at least a part of the compounds (I. a) and (l.b) is derived from gallic acid, shikimic acid or 3- dehydroshikimic acid which is obtained from a renewable source and / or is derived from an alkanol R6OH or an amine NHR7R8which is obtained from a renewable source.

[0146] E.70. The compound according to embodiment E.69, where in the compounds (I. a) and (l.b) at least 20 mol-% of the carbon atoms, relative to the total amount of carbon atoms in the compounds (I. a) and (l.b), stem from a renewable source.

[0147] E.71. A method for preparing a compound of the formula (I. a) as defined in any of embodiments E.1 to E.30, E.32 to E.34 or E.41 , E.44 to E.52 and E.55 to E.70, wherein one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other of R4and R5is hydrogen, comprising (i.1) reacting a compound (II) where Y is as defined in any of embodiments E.1 or E.19 to E.28 or E.41 and E.60 to E.68 and R1ais oxo or OR1aa, where R1aais hydrogen, with a sulfonation agent; and (ii.1) if desired reacting the compound (I. a) obtained in step (i.1) with a base to obtain a compound (I. a) wherein one of R4and R5is a group -S(O)3'M+and the other of R4and R5is hydrogen, and where optionally also one of R1aa(if present) R2aand R3ais a group -S(O)3'M+.

[0148] E.72. A method for preparing a compound of the formula (I. a) as defined in any of embodiments E.1 to E.30, E.32 to E.34 or E.41 , E.44 to E.52 and E.55 to E.70, wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3aa group -S(O)3H or -S(O)3'M+, comprising (i.2) reacting a compound (III) where Y is as defined in any of embodiments E.1 or E.19 to E.28 or E.41 and E.60 to E.68 and R1ais oxo or OR1aa, where R1aais hydrogen, with a sulfonation agent to obtain a compound (I. a) wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3ais a group -S(O)3H; and

[0149] (ii.2) if desired reacting the compound (I. a) obtained in step (i.2) with a base to obtain a compound (I. a) wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3ais a group -S(O)3'M+.

[0150] E.73. The method according to any of embodiments E.71 or E.72, where the sulfonation agent is selected from the group consisting of hydrogensulfites, chlorosulfonic acid, sulfur trioxide (SO3), mixtures of sulfur trioxide (SO3) with air; sulfamic acid, and oleum (fuming sulfuric acid; sulfuric acid with excess sulfur trioxide).

[0151] E.74. The method according to any of embodiments E.71 or E.73, where the sulfonation agent is selected from the group consisting of hydrogensulfites.

[0152] E.75. The method according to embodiment E.74, where the sulfonation agent is selected from the group consisting of alkali metal hydrogensulfites.

[0153] E.76. The method according to embodiment E.75, where the sulfonation agent is sodium hydrogensulfite.

[0154] E.77. The method according to any of embodiments E.72 or E.73, where the sulfonation agent is selected from the group consisting of chlorosulfonic acid, sulfur trioxide (SO3), mixtures of sulfur trioxide (SO3) with air; sulfamic acid, and oleum (fuming sulfuric acid; sulfuric acid with excess sulfur trioxide). E.78. The method according to any of embodiments E.71 to E.77, where the base is selected from alkali or alkaline earth metal hydroxides, alkali or alkaline earth metal carbonates, alkali or alkaline earth metal hydrogencarbonates, alkali or alkaline earth metal phosphates or ammonia.

[0155] E.79. The method according to embodiment E.78, where the base is selected from alkali metal hydroxides.

[0156] E.80. The method according to embodiment E.79, where the base is selected from NaOH and KOH.

[0157] E.81. The method according to embodiment E.80, where the base is NaOH.

[0158] Unless specified otherwise, the above and below remarks to suitable and preferred compounds (I. a) and (l.b) and compositions in which these are used apply both to the uses of the inventions as well as to the methods of use the invention and the compositions of the invention.

[0159] Use as surfactants

[0160] In a preferred embodiment, in compounds (I. a) one of R4and R5is -S(O)3H or -S(O)3'M+, more preferably -S(O)3'M+; and the other of R4and R5is hydrogen.

[0161] In another preferred embodiment, in compounds (I. a)

[0162] R1ais a group -OR1aaor an oxo group (=0); and

[0163] R1aa, R2a, R3a, R4and R5are hydrogen; or one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen; and R1aa, R2aand R3a, independently of each other, are hydrogen or a group -S(O)3H or -S(O)3'M+; where more preferably one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen.

[0164] In another preferred embodiment, in compounds (I. a)

[0165] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0166] R1ais oxo and at least one of R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3'M+; or

[0167] R1ais OR1aaand at least one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3-M.

[0168] More preferably, in compounds (I. a)

[0169] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0170] R1ais oxo, one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen, and R2aand R3aare independently hydrogen or a group -S(O)3H or -S(O)3'M+; or R1ais OR1aa, one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen, and R1aa, R2aand R3aare independently hydrogen or a group -S(O)3H or -S(O)3-M+.

[0171] In another more preferred embodiment, in compounds (I. a) R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or R1ais oxo and on average one of R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+; and the other three of R2a, R3a, R4and R5are hydrogen, or R1ais OR1aaand on average one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+; and the other four of R1aa,R2a, R3a, R4and R5are hydrogen.

[0172] “On average” means to express that not all compounds (I. a) contain exactly one group -S(O)3H or -S(O)3'M+. A part of the compounds (I. a) may contain two groups -S(O)3H or -S(O)3'M+and a part no such groups. Compounds (I. a) wherein on average one of R2a, R3a, R4and R5or wherein on average one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+are obtainable in technical processes, e.g. by reacting a compound (l.b) wherein all of R1bb(if present) R2b, R3bare hydrogen with a sulfonation agent. The resulting product is principally a compound (I. a) wherein exactly one of R2a, R3a, R4and R5or wherein exactly one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+; but depending on the reaction conditions, the product may also contain minor amounts of compounds (I. a) wherein two and none of these radicals are a group -S(O)3H or -S(O)3'M+. Compounds (I. a) wherein exactly one of R2a, R3a, R4and R5or wherein exactly one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+may be isolated from such mixtures, but for the purpose of the present invention this is not necessary, and such mixtures can be used as well. Generally, the amount of compounds (I. a) wherein two and none of these radicals are a group -S(O)3H or -S(O)3'M+is not large anyway.

[0173] Even more preferably, in compounds (I. a)

[0174] R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, or

[0175] R1ais oxo, one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen, and R2aand R3aare hydrogen, or

[0176] R1ais OR1aa, one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen, and R1aa, R2aand R3aare hydrogen.

[0177] Particularly preferably, in compounds (I. a) one of R4and R5is -S(O)3'M+and the other of R4and R5is hydrogen; R2aand R3aare hydrogen; and R1ais oxo or OR1aa, wherein R1aais hydrogen. More particularly, in compounds (l.a) one of R4and R5is -S(O)3'M+and the other of R4and R5is hydrogen; R2aand R3aare hydrogen; and R1ais OR1aa, wherein R1aais hydrogen.

[0178] Due to the preparation method preferably applied for preparing compounds (I. a) (see below), among R4and R5, the -S(O)3H or -S(O)3'M+group is preferably in the position of R5, and R4is thus preferably hydrogen.

[0179] Preferably, in compounds (l.b)

[0180] R1bis oxo and R2band R3bare hydrogen; or

[0181] R1bis OH and R2band R3bare hydrogen.

[0182] More preferably, in compounds (l.b) R1bis OH and R2band R3bare hydrogen.

[0183] Among compounds (la.) and (l.b), preference is given to compounds (I. a).

[0184] In view of their use as surfactants, in compounds (I. a) and (l.b), among groups -S(O)3H and -S(O)3'M+preference is given to group -S(O)3'M+.

[0185] As explained above, the compounds (l.a) and (l.b) have several stereogenic centers and can be present in the form of various stereoisomers or stereoisomeric mixtures. As also explained above, the compounds (l.a) and (l.b) are preferably derived from shi- kimic acid (formula A) or 3-dehydro shikimic acid (formula B):

[0186] Accordingly, preferred stereoisomers and stereoisomeric mixtures of the compound of the formula (I. a) are compounds of the formula (l.a.1), (I. a.2) or (I. a.3), and preferred stereoisomers and stereoisomeric mixtures of the compound of the formula (l.b) are compounds of the formula (l.b.1), (l.b.2) or (l.b.3). Preferably, the compound of the formula (l.a) is a compound of the formula (I .a.1 ), (I. a.2) or (I. a.3). Preferably, the compound of the formula (l.b) is a compound of the formula (l.b.1), (l.b.2) or (l.b.3).

[0187] Preferably, M+is an alkali metal cation or an alkaline earth metal cation equivalent, more preferably Na+, K+, (Mg2+)i / 2 or (Ca2+)i / 2, in particular Na+or K+, and is specifically Na+.

[0188] In a preferred embodiment, Y in compounds (I. a) and (l.b) is -OR6.

[0189] In another preferred embodiment, Y in compounds (I. a) and (l.b) is -NR7R8.

[0190] More preference is however given to Y being -OR6.

[0191] Preferably, R6and R7, independently of each other, are Cs-Cso-alkyl, more preferably Cio-Ci8-alkyl, even more preferably Cio-Ci4-alkyl. R7is preferably hydrogen.

[0192] Since it is desired to provide surfactants which are obtained at least partly from renewable sources, especially from bio-based sources, it is preferred that Y be derived from such a source. The group OR6is for example derived from an alcohol R6OH. Renewable, to be more precise bio-based sources for such alcohols are for example fats and oils of animal or vegetal origin, which triglycerides can be hydrolized and the resulting fatty acids reduced to fatty alcohols. The fatty acids can alternatively be converted into fatty amines. Most fatty acids obtained from natural oils and fats contain linear alkyl or alkenyl chains. Moreover, linear alkyl or alkenyl chains are generally better biodegradable than branched residues.

[0193] Accordingly, in a preferred embodiment, R6and R7, independently of each other, are linear Cs-Cso-alkyl, more preferably linear C -Cis-alkyl, and in particular linear Cw-C - alkyl.

[0194] Most alkyl or alkenyl chains contained in fatty acids obtained from natural oils and fats are of an even carbon number.

[0195] Moreover alkyl or alkenyl chains with an even carbon number are generally better biodegradable than alkyl or alkenyl chains with an odd carbon number.

[0196] Accordingly, in a preferred embodiment, R6and R7, independently of each other, are linear Cs-Cso-alkyl with an even carbon number, more preferably linear Cw-Cu-alkyl with an even carbon number, and in particular linear Cw-Cu-alkyl with an even carbon number.

[0197] In particular, R6and R7, independently of each other, are n-decyl, n-dodecyl, n- tetradecyl, n-hexadecyl or n-octadecyl, and more particularly n-decyl, n-dodecyl or n- tetradecyl. Specifically, R6and R7are n-dodecyl.

[0198] In each case, R8is preferably hydrogen.

[0199] In a particular embodiment, in compound (I. a), one of R4and R5is -S(O)3H or -S(O)3‘ M+, preferably -S(O)3'M+; and the other of R4and R5is hydrogen; R2aand R3aare hydrogen; R1ais oxo or OR1aa, wherein R1aais hydrogen; Y is OR6and R6is Cw-C -alkyl. More particularly, one of R4and R5is -S(O)3'M+, where M+is an alkali metal cation; and the other of R4and R5is hydrogen; R2aand R3aare hydrogen; R1ais OR1aa, wherein R1aais hydrogen; Y is OR6and R6is Cw-C -alkyl. If Y is derived from a bio-based source, R6is preferably linear Cw-C -alkyl, specifically n-decyl, n-dodecyl or n- tetradecyl and very specifically n-dodecyl.

[0200] In a particular embodiment, in compound (l.b) R1bis OH, R2band R3bare hydrogen, Y is OR6and R6is Cw-C -alkyl. If Y is derived from a bio-based source, R6is preferably linear Cw-C -alkyl, specifically n-decyl, n-dodecyl or n-tetradecyl and very specifically n-dodecyl.

[0201] As said, it is desired to provide surfactants which are obtained at least partly from renewable sources, especially from bio-based sources. Renewable sources are sources that theoretically may be inexhaustible. They are natural and self-replenishing, and usually have a low- or zero-carbon footprint. Among these, bio-based sources, i.e. non-fossil materials of vegetal or animal origin, are of major importance.

[0202] However, also upcycled Ci “exhaust gases” which would otherwise be released into the atmosphere, such as CO2 or methane, are considered as a renewable source.

[0203] Preference is however given to bio-based sources.

[0204] In a preferred embodiment, at least a part of the compounds (I. a) and (l.b) is derived from gallic acid, shikimic acid or 3-dehydroshikimic acid which are obtained from a renewable, preferably bio-based, source and / or is derived from an alcohols R6OH or an amine NHR7R8which is obtained from a renewable, preferably bio-based, source.

[0205] More preferably in the compounds (I. a) and (l.b) at least 20 mol-%, in particular at least 30 mol-%, especially at least 50 mol% or up to 100 mol-% of the carbon atoms, relative to the total amount of carbon atoms in the compounds (I. a) and (l.b), stem from a renewable source. Even more preferably, in the compounds (I. a) and (l.b) at least 20 mol-%, in particular at least 30 mol-%, especially at least 50 mol% or up to 100 mol-% of the carbon atoms, relative to the total amount of carbon atoms in the compounds (I. a) and (l.b), are bio-based.

[0206] Gallic acid, from which compounds (I. a) and (l.b) can be prepared (for further details see below description of the synthesis methods of the invention), is found in many plants and plant parts (e.g. in divi-divi (Caesalpinia coriaria), oak bark, gallnuts, pomegranate roots, sumac or tea). The acid occurs free or bound to tannin. Gallic acid is for example produced from tannin-rich aqueous gallnut extracts by acidic or alkaline hydrolysis. Alternatively, it is obtained by fermentative processes from tannin, using the enzyme tannase or molds (Penicillium glaucum; Aspergillus niger); or by fermentation of sugars or other digestible carbohydrates according to well established methods.

[0207] Shikimic acid, from which compounds (I. a) and (l.b) can be prepared (for further details see below description of the synthesis methods of the invention), is found for example in large quantities in the shikimi fruit and in the related star anise, but can also be synthesized using recombinant E. coli strains or by fermentation of sugars or other digestible carbohydrates according to well established methods.

[0208] 3-Dehydroshikimic acid, from which compounds (I. a) and (l.b) can be prepared (for further details see below description of the synthesis methods of the invention) is also obtainable by fermentation of sugars or other digestible carbohydrates according to well established methods...

[0209] Fatty alcohols R6OH or fatty amines NHR7R8are obtainable from fats and oils of vegetal or animal origin, as described above.

[0210] The origin of the compounds (I. a) and (l.b) from a renewable, to be more precise a biobased source can be verified, for example, by radiocarbon dating. Radiocarbon dating is based on the fact that radiocarbon (14C) is constantly created in the earth's atmosphere by the interaction of cosmic rays with atmospheric nitrogen: The cosmic rays generate neutrons in the atmosphere which can strike nitrogen-14 (14N) atoms. These, in turn, decay to14C under release of a proton. The resulting14C combines with atmospheric oxygen to form radioactive carbon dioxide, which is incorporated into plants by photosynthesis, subsequently into herbivorous animals feeding on plants and ultimately into the complete biosphere by carnivorous animals feeding on herbivorous animals. Upon death of the animal or plant, carbon exchange with its environment is stopped, whereupon the amount of14C begins to decrease as the14C undergoes radioactive decay.

[0211] Measuring the amount of14C in a sample of a compound (I. a) or (l.b) is thus an indicator of its origin: In compounds (I. a) and (l.b) which are derived completely from a renewable, to be more precise from a bio-based source, the amount of14C will be the same or not essentially lower than found in presently living organisms.

[0212] Generally, the molar ratio of the12C isotope to the14C isotope is used as an indicator. In living organisms, the molar ratio of the12C isotope to the14C isotope is approximately 1 X 1012: 1 (to be more precise 1 x1012: 1.25).

[0213] Thus, the content of the14C isotope in the compound (I. a) or (l.b) will be at a detectable level if at least part of the compound (I. a) or (l.b) is derived from a renewable, to be more precise from a bio-based source. Suitable methods for determining the content of the14C isotope are known in the art and deliver generally comparable results. For example, the method according to ASTM D6866-21 can be used; this method was specifically developed for determining the content of bio-based / biogenic carbon in bioproducts. However, other methods are suitable as well. The detection level of the available methods of the content of the14C isotope is such that it allows radiocarbon dating between ca. 300 and 60000 before the present time, which is very remote from the age of fossil carbon sources. Thus, any detected14C isotope is an indicator of a renewable origin of the compound (I. a) or (l.b). In a preferred embodiment, the molar ratio of the12C isotope to the14C isotope in the compounds (I. a) and (l.b) is less than 3x1012: 1 , i.e. it is from ca. 1 xio12: 1 (to be more precise from 1 x 1 o12: 1.25) to less than 3x 1012: 1 .

[0214] Compounds (I. a) and (l.b) are obtainable by standard methods of organic chemistry.

[0215] Compounds (I. a) wherein R1ais OH and R2a, R3a, R4and R5are hydrogen are for example obtainable by esterification or amidation of gallic acid or a more reactive derivative thereof, such as its acid halide or anhydride, followed by hydrogenation of the phenyl ring. Reaction thereof with a sulfonation agent affords compounds (I. a) wherein at least one of R1aa, R2aand R3ais a group -S(O)3H. If desired, subsequent neutralization affords compounds (I. a) wherein at least a part of the -S(O)3H groups are converted into a

[0216] -S(O)3'M+group.

[0217] Alternatively, compounds (I. a) wherein R1ais OH and R2a, R3a, R4and R5are hydrogen are for example obtainable by esterification or amidation of shikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride, followed by hydrogenation of the C-C double bond. Reaction thereof with a sulfonation agent affords compounds (I. a) wherein at least one of R1aa, R2aand R3ais a group -S(O)3H. If desired, subsequent (or simultaneous) neutralization affords compounds (I. a) wherein at least a part of the -S(O)3H groups are converted into a -S(O)3'M+group.

[0218] Compounds (I. a) wherein R1ais oxo and R2a, R3a, R4and R5are hydrogen are for example obtainable by esterification or amidation of 3-dehydroshikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride, followed by hydrogenation of the C-C double bond

[0219] Compounds (I. a) wherein one of R4and R5is a group -S(O)3H or -S(O)3'M+, R1ais OR1aand R1aa, R2aand R3aare hydrogen or a group -S(O)3H or -S(O)3'M+, are for example obtainable by esterification or amidation of shikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride. Subsequent reaction of the obtained shikimic acid ester or amide with a sulfonation agent affords compounds (I. a) wherein one of R4and R5is a group -S(O)3H and optionally also one or more of R1aa, R2aand R3aare -S(O)3H (those of R1aa, R2aand R3anot being -S(O)3H are H). If desired, subsequent (or simultaneous) neutralization affords compounds (I. a) wherein at least a part of the -S(O)3H groups are converted into a -S(O)3'M+group. Compounds (I. a) wherein one of R4and R5is a group -S(O)3H or -S(O)3'M+, R1ais oxo and R2aand R3aare hydrogen or a group -S(O)3H or -S(O)3'M+, are for example obtainable by esterification or amidation of 3-dehydroshikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride. Subsequent reaction of the obtained 3-dehydroshikimi acid ester or amide with a sulfonation agent affords compounds (I. a) wherein one of R4and R5is a group -S(O)3H and optionally also one or both of R2aand R3aare -S(O)3H (those of R2aand R3anot being -S(O)3H are H). If desired, subsequent (or simultaneous) neutralization affords compounds (I. a) wherein at least a part of the -S(O)3H groups are converted into a -S(O)3'M+group.

[0220] Compounds (l.b) wherein R1bis OH and R2band R3bare hydrogen are for example obtainable by esterification or amidation of shikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride.

[0221] Compounds (l.b) wherein R1bis oxo and R2band R3bare hydrogen are for example obtainable by esterification or amidation of 3-dehydroshikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride.

[0222] Further details to the preparation of compounds (I. a) and (l.b), especially the sulfonation reaction, are given in context with the synthetic methods of the invention.

[0223] As said, the compounds of the formulae (I. a) and (l.b) are suitable as surfactants, in particular as emulsifiers, as foam regulators and / or as wetting agents. They can be used as surfactants in a wide variety of applications, including, but not limited to detergents, including laundry detergents, dishwashing detergents and hard surface cleaners in homecare as well as in l&l applications, in humectants, in cosmetic and pharmaceutical formulations, in crop protection formulations, in coating agents, in adhesives, in sealant compositions, in leather degreasing agents, in formulations for the textile industry, in fiber processing, in metal processing, in the food industry, for water treatment, in paper industry, in fermentation processes, for mineral processing and in emulsion polymerizations. They may be used in any composition which typically contain at least one surfactant. In these compositions, the may partly or completely replace conventional surfactants, in particular anionic surfactants.

[0224] Preferably, they are used in homecare compositions, l&l cleaning compositions, personal care compositions or pesticide adjuvant compositions. In another preferred embodiment, they are used for stabilizing oil-in-water emulsions or aqueous dispersions. Further details are given in context with the composition of the invention.

[0225] Method for

[0226] The invention also relates to a method for cleaning or washing a surface or a material, comprising bringing the surface or material into contact with a compound (I. a) or (l.b) or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b); or with a composition containing a compound (I. a) or (l.b) or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b), e.g. with the above-mentioned surfactant composition.

[0227] The above remarks, explanations and preferred embodiments mentioned for compounds (I. a) and (l.b) in context with the use according to the invention apply here analogously. Suitable composition containing a compound (I. a) or (l.b) or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b) are described below in more detail. Surfaces or materials to be cleaned or washed will also become apparent from the below details; the include laundry, textiles in general, dishes, hard surfaces (e.g. glass, floor, counter, bath(room), toilet bowl, sink, kitchen, appliance, furniture etc.), body parts (e.g. skin, hair), etc.

[0228] Surfactant

[0229] The present invention also relates to a surfactant composition comprising a compound of the formula (I. a) or (l.b) as defined above or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b); and at least one component selected from the group consisting of: water, organic solvents, surfactants different from the compounds (I. a) and (l.b), fragrances, antimicrobial agents, sequestrants, enzymes, enzyme stabilizers, hydrotropic agents, bleaching agents, dyes, pigments, pH adjusting agents, pearlescents, opacifiers, viscosity modifiers, and inorganic salts.

[0230] The above remarks, explanations and preferred embodiments mentioned for compounds (I. a) and (l.b) in context with the use according to the invention apply here analogously.

[0231] However, in an embodiment, the composition according to the invention does not comprise any of C6-Ci2-alkylesters of shikimic acid, C6-Ci2-alkylesters of 3-dehydroshikimic acid, N-hexadecyl shikimic acid amide and N-tridecyl shikimic acid amide. The surfactant compositions of the invention include homecare compositions, including detergent formulations, such as laundry detergents, dishwashing detergents and household cleaners (e.g. hard surface cleaners), compositions for cleaning or disinfecting on an industrial scale (also called industrial and institutional cleaning or l&l cleaning), personal care compositions, compositions for metal processing, such as metal working fluids, compositions for fibre processing, compositions for paper production processes, leather degreasing agents, humectants, aqueous polymer dispersions (polymer latexes or polymer emulsions), slurries of inorganic or organic matter, such as pigment compositions, coating compositions, such as paint formulations, varnishes and stains, crop protection compositions, adhesive formulations, sealant formulations etc.

[0232] Therefore, the present invention in particular relates to homecare compositions, cleaning agents, including household cleaners and l&l cleaners, wetting agents, coating compositions, adhesive compositions, leather degreasing agents, humectants, textile treatment agents, pigment compositions, sealant formulations, and cosmetic, pharmaceutical or crop protection formulations containing a compound of formula (I. a) and (l.b). The compounds (I. a) and (l.b) are particularly suitable as surfactants in homecare compositions, l&l cleaning compositions, personal care compositions and crop protection compositions, e.g. in pesticide adjuvant compositions.

[0233] Homecare compositions are generally understood to be compositions for cleaning or washing goods and objects. Homecare compositions and compositions for cleaning or disinfecting on an industrial scale (also called industrial and institutional cleaning or l&l cleaning) overlap largely, only that l&l compositions are adapted to the use on a larger scale and are thus often more aggressive (e.g. by being more concentrated and / or by having a distinctly higher or lower pH than the respective homecare composition) and / or are less “pleasant”, e.g. in the sense of odor or aspect or touch. Moreover, they are suitable for clean-in-place (CIP), which is a method of automated cleaning the interior surfaces of pipes, vessels, equipments, filters and associated fittings and the like without major disassembly.

[0234] Examples for homecare and l&l compositions are dishwashing compositions, laundry compositions (for example laundry detergents, fabric softeners, rinsing compositions, bleacher compositions, stain remover compositions and the like), surface cleaning compositions (also termed hard surface cleaners; for example glass, floor, counter, bath(room), toilet bowl, sink, kitchen, appliance and furniture cleaning compositions; all-purpose cleaners; sanitary cleaners), non-cosmetic deodorants (e.g. air and / or surface deodorants), disinfectants (for example spray air disinfectants, and spray, liquid and paste / gel surface disinfectants), surface protecting and / or polishing compositions, rug shampoos, descaling agents, and compositions for wet wipes (e.g. for cleaning the floor, furniture, bath room surfaces etc.).

[0235] Personal care compositions are used for cleaning, washing, disinfecting, nurturing, grooming, protecting or embellishing the human body (and thus also include cosmetics). Examples are creams, lotions, ointments, other o / w or w / o emulsions, liquid or gellike soaps, shampoos, make-up and other decorative cosmetics, and compositions for wet wipes (e.g. for cleaning the nappy area). More specific examples are skin-washing and cleansing preparations in the form of soaps, syndets, washing gels, soapless detergents or washing pastes, bath preparations, e.g. foam baths, milks, oils, shower preparations; skin-care preparations, e.g. skin emulsions, multi-emulsions, powders, sprays or skin oils; cosmetic preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nailcare preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations; light- protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; skin-tanning preparations, e.g. self-tanning creams; depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations; insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks; deodorants, such as deodorant sprays, deodorant aerosols, pump-action sprays, deodorant gels, sticks or roll-ons, also water-free deodorant aerosols or sticks; antiperspirants, e.g. antiperspirant sticks, creams or roll-ons; preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks; hair-removal preparations in chemical form (depilation), e.g. liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams; shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, pre-shave preparations for dry shaving, aftershaves or aftershave lotions; fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams; cosmetic hairtreatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hairsetting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colorants, preparations containing self- oxidising dyes, or natural hair colorants, such as henna or camomile; antidandruff preparations in the form of shampoos, conditioners, hair tonics, styling creams or gels or treatments packs; oral care preparations such as (tooth) pastes, gels, mouth washes and sprays; disinfectants for mouth or skin.

[0236] Crop protection compositions, which are often also termed plant protection compositions, are compositions which are effective against various harmful microorganisms, harmful invertebrate pests or undesired plants relevant for agriculture, e.g. harmful fungi, harmful invertebrate pests, such as harmful insects, arachnids, nematodes or molluscs, and weeds, which cause damage to agricultural plants, plant propagation materials, such as seeds, or harvested crops. Examples for crop protection compositions are fungicidal, insecticidal, acaricidal, nematicidal, moluscicidal or herbicidal compositions and pesticide adjuvant compositions. Crop protection compositions also encompass plant growth regulating compositions. Plant growth regulators are plant protection products used to influence plant growth and are used, for example, for increasing the stability of cereals by shortening the stalk length, thus reducing or preventing lodging, for improving the rooting of cuttings, reducing plant height in horticulture, preventing the germination of potatoes and the like. The term encompasses moreover compositions used in material protection for combating various harmful microorganisms and invertebrate pests, such as compositions for the treatment of lumber or the surroundings of lumber material against termites or compositions for the treatment of mosquito nets against harmful insects, such as Anopheles mosquitoes, and the like.

[0237] The compositions of the invention contain, in addition to compounds (I. a) and / or (l.b), at least one further component, namely at least one of: water, organic solvent, surfactant different from the compounds (I. a) and (l.b), fragrance, antimicrobial agent, se- questrant, enzyme, enzyme stabilizer, hydrotropic agent, bleaching agent, dye, pigment, pH adjusting agent, pearlescent, opacifier, viscosity modifier, inorganic salt.

[0238] Suitable organic solvents are for example Ci-Cs-alkanols (e.g. ethanol, n-propanol or isopropanol), C2-Cs-alkanediols (e.g. ethylene glycol, propylene glycol, 1 ,2 hexanediol, 2-ethyl-1 ,3-hexanediol and 2,2,4-trimethyl-1 ,3-pentanediol), Ci-Cs-alkylmonoethers of C2-Cs-alkanediols In particular the Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol, e.g. ethylene glycol mono-n-butyl ether (= butylglyol), propylene glycol mono-n-butyl ether), polyetherpolyols (e.g. polyethylene glycol, polypropyleneglycol), Ci-Cs-alkylmonoethers of polyetherpolyols (e.g. polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol mono-n-propyl ether, polyethylene glycol mono-n-butyl ether), and mixtures thereof

[0239] Surfactant different from the compounds (I. a) and (l.b) can be anionic, non-ionic, cationic or amphotheric (zwitterionic). Anionic surfactants are, for example, of the sulfate, sulfonate or carboxylate type or mixed forms thereof. Examples are alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to an alpha-sulfonic fatty acid salt or an ester thereof.

[0240] More specific examples are alkylbenzenesulfonates having from 10 to 20 carbon atoms in the alkyl radical (e.g. sodium dodecylbenzene sulfonate), alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical (e.g. sodium lauryl sulfate), alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical (e.g. sodium laureth sulfate;

[0241] SLES), and fatty acid salts derived from oils or fats, e.g. from palm oil or tallow and having from 8 to 18 carbon atoms in the alkyl moiety (thus containing, inter alia, sodium oleate, linolate, palmitate, myristate, stearate etc.). The counter-cation is preferably an alkali metal cation, especially sodium or potassium, specifically sodium. Preferred carboxylates are alkali metal sarcosinates of formula R-CON(R’)CH2COO'M+wherein R’ is Cg-Ci7-alkyl or Cg-Cn-alkenyl, R’ is Ci-C4-alkyl and M+is an alkali metal cation, especially Na+.

[0242] Non-ionic surfactants are, for example, a primary or secondary alcohol ethoxylate, especially a C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 mol of ethylene oxide per alcohol group. Preference is given to primary and secondary C10-C15 aliphatic alcohols ethoxylated with an average of from 1 to 10 mol of ethylene oxide per alcohol group. Non-ethoxylated non-ionic surfactants, for example alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamide), may likewise be used.

[0243] Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines, for example Ce-Cis-alkyl betaines (e.g. cocoamidopropyl betaine; disodium cocoam- phodiacetate (DSCADA)) or Ce-Cis-alkyl sulfobetaines, or amine oxides such as alkyldimethylamine oxides.

[0244] Cationic surfactants are, for example, ammonium salts such as Cs-Cie-dialkyldime- thylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical.

[0245] Fragrances can be of natural or synthetic origin; their nature is in general not critical. Just by way of example, natural aromatic substances are, for instance, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Also just by way of example, synthetic aromatic substances are, for instance, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclo- hexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and ben-'zyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamalde- hyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, am- broxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, damascene, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.

[0246] Further examples are alpha-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate (Pheni- rat1), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably having a cis-isomer content of more than 60 wt.%) (Hedione9, Hedione HC9), 4,6,6,7,8,8-hexamethyl-1 ,3, 4, 6, 7, 8- hexahydrocyclopenta[g]benzopyran (Galaxolide3), tetrahydrolinalool (3,7-dimethyloctan-3-ol), ethyl linalool, benzyl salicylate, 2-methyl-3- (4-tertbutylphenyl)propanal (Lilial2), cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a-hexa- hydro-5-indenyl acetate and / or 4,7-methano-3a,4,5,6,7,7a hexahydro-6-indenyl acetate (Herbaflorat1), citronellol, citronellyl acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styralyl acetate (1 -phenylethyl acetate), octahydro-2, 3,8, 8-tetramethyl-2-acetonaph- thone and / or 2-acetyl-1 ,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (Iso E Super3), hexyl salicylate, 4-tert-butylcyclohexyl acetate (Oryclone1), 2-tert-butylcyclo- hexyl acetate (Agrumex HC1), alpha-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3- buten-2-one), nalpha- methylionone, alpha-isomethylionone, coumarin, terpinyl acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4-methylpentyl)-3- cyclohexenecarboxaldehyde (Lyral3), alphaamylcinnamaldehyde, thylene brassylate, (E)- and / or (Z)-3-methylcyclopentadec-5-enone (Muscenone9), 15-pentadec-11-enolide and / or 15-pentadec-12-enolide (Globalide1), 15-cyclopentadecanolide (Macrolide1), 1- (5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthalenyl)ethanone (Tonalide10), 2- isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol9), 2-ethyl-4-(2,2,3-trimethyl-3-cyclo- penten-1-yl)-2-buten-1-ol (Sandolene1), cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2-cis--6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral1), 2,4,4,7-tetramethyl-oct-6-en-3-one (Claritone1), 2,6-dimethyl-5-hepten-1-al (Melonal2), borneol, 3-(3-isopropylphenyl)butanal (Florhydral2), 2-methyl-3-(3,4-methylenedioxy- phenyl)propanal (Helional3), 3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon1), 7-me- thyl-2H-1 ,5-benzodioxepin-3(4H)-one (Calone19515), 3,3,5-trimethylcyclohexyl acetate (preferably with a content of cis-isomers of 70 wt.%) or more and 2,5,5-trimethyl- 1 ,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol S1).

[0247] If trade names are specified above, these refer to the following sources:

[0248] 1Trade name of Symrise GmbH, Germany;

[0249] 2Trade name of Givaudan AG, Switzerland;

[0250] 3Trade name of International Flavors & Fragrances Inc., USA;

[0251] 5Trade name of Danisco Seillans S.A., France;

[0252] 9Trade name of Firmenich S.A., Switzerland;

[0253] 10Trade name of PFW Aroma Chemicals B.V., The Netherlands.

[0254] The fragrances may optionally be incorporated in encapsulated form.

[0255] Suitable antimicrobial agents are for example 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether (diclosan), 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde, 2,4-dichlorobenzylalcohol, 1 ,3,5-tris-(2-hydroxyethyl)-1 ,3,5- hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, isothiazolinones, e.g. 1 ,2-benziso- thiazol-3(2H)-one (BIT), 2-methyl-2H-isothiazol-3-one (MIT), 2-octyl-2H-isothiazol-3- one (OIT), 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT), or 2-butyl-benzo[d]isothiazol- 3-one (BBIT); 3-iodo-2-propynylbutylcarbamate (IPBC), benzyl alcohol, pyridine-2-thiol 1-oxide and salts thereof; 2,2-dibromo-2-cyanoacetamide (DBNPA), N-(3-aminopro- pyl)-N-dodecylpropane-1 ,3-diamine (Diamine), tetrakis(hydroxymethyl)phosphonium sulphate(2:1) (THPS), 2,2-dithiobis[N-methylbenzamide] (DTBMA), 2-bromo-2-(bromo- methyl)pentanedinitril (DBDCB), biphenyl-2-ol (synonyms 2-phenylphenol, o-phe- nylphenol) and salts thereof, benzalkonium chloride; and mixtures thereof.

[0256] Sequestrants, also termed builders, structural substances, framework substances, complexing agents, chelators, chelating agents or softeners, bind alkaline earth metals and other water-soluble metal salts without precipitating. They help to break up soil, disperse soil components, help to detach soil and in some cases themselves have a washing effect. Many of the sequenstrants listed below are multi-functional, meaning that the substances have additional functions, such as a dispersing activity or anti-grey- ing properties.

[0257] Suitable sequestrants may be either organic or inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, e.g. hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and salts thereof, and polymeric compounds containing carboxylic acid groups and salts thereof.

[0258] Suitable inorganic sequestrants are, for example, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as zeolites. Crystalline silicates suitable as sequestrants are, for example, disilicates or sheet silicates, e.g. 5-Na2Si20s or B- Na2Si2C>5 (SKS 6 or SKS 7). Suitable inorganic sequestrant substances based on carbonate are carbonates and hydrogencarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Customary phosphates used as inorganic sequestrants are alkali metal orthophosphates and / or polyphosphates, for example pentasodium triphosphate.

[0259] Suitable organic sequestrants are, for example, C4-C3o-di-, -tri- and -tetracarboxylic acids, for example succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and alkyl- and alkenylsuccinic acids with C2-C2o-alkyl or -alkenyl radicals. Suitable organic sequestrants are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C4-C20-hydroxycarboxylic acids, for example malic acid, tartaric acid, glutonic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid, and sucrose- mono-, -di- and -tricarboxylic acid. Among these, preference is given to citric acid and salts thereof. Suitable organic sequestrants are also phosphonic acids, for example hydroxyalkylphosphonic acids or aminophosphonic acids, and the salts thereof. These include, for example, phosphonobutanetricarboxylic acid (2-phosphinobutane-1 ,2,4-tri- carboxylic acid; PBTC), aminotris-methylenephosphonic acid (N[CH2PO(OH)2]3), ami- notris(methylenephosphonate), sodium salt (ATMP; N[CH2PO(ONa)2]3), ethylenedia- minetetra(methylenephosphonic acid) (EDTMPA), hexamethylenediamine(tetramethy- lenephosphonic acid), hexamethylenediamine(tetramethylenephosphonate), potassium salt (CIOH(28-X)N2KXOI2P4 (X=6)), bis(hexamethylene)triamine(pentamethylene- phosphonic acid) ((HO2)POCH2N[(CH2)2N[CH2PO(OH)2]2]2), diethylenetriamine-penta- (methylenephosphonic acid) (DTPMP; (HO)2POCH2N[CH2CH2N[CH2PO(OH)2]2]2), di- ethylenetriaminepenta(methylenephosphonate), sodium salt (CgH^s-xjNsNaxOisPs (x=7)); tetramethylene-triamine-pentaphosphonic acid, hydroxyethylamine diphos- phonic acid, 2-hydroxyethyliminobis(methylenephosphonic acid) (HOCH2CH2N[CH2PO(OH)2]2), morpholinomethanediphosphonic acid, 1-hydroxy-Ci- to Cw-alkyl-1 , 1 -diphosphonic acids such as 1-hydroxyethane-1 ,1-diphosphonic acid (HEDP; CH2C(OH)[PO(OH)2]2). Suitable organic sequestrants are moreover polyas- paratic acids. Polyaspartic acid include salts of polyaspartic acids. Salt forming cations may be monovalent or multivalent, examples being sodium, potassium, magnesium, calcium, ammonium, and the ammonium salt of mono-, di- and triethanolamine. Such polymers may be co-polymers, in particular of (a) L- or D-aspartic acid (preferably L- aspartic acid), (b) a carboxylic acid and (c) a diamone or an amino alcohol. Such copolymers generally comprise 70-95 mol% of (a), 5-30 mol% of (b) and 2-20 mol% of (c). The molar ratio of the carboxyl-containing compound (b) to the diamine or amino alcohol (c) is preferably between 5:1 and 1 :1.5 or between 3:1 and 1 :1.2, and more preferably between 3:1 and 1 :1 or 2:1 and 1 :1. Suitable organic sequestrants are additionally aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid, nitrilotripropionic acid, p-alaninediacetic acid (p-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, 1 ,3-propylenediaminetet- raacetic acid, 1 ,2-propylenediaminetetraacetic acid, N-(alkyl)ethylenediaminetriacetic acid, N-(hydroxyalkyl)ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cy- clohexylene-1 ,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediaminedisuccinic acid, serinediacetic acid, isoserinediacetic acid, L-asparaginediacetic acid, L-glu- taminediacetic acid, methylglycinediacetic acid (MGDA), and the salts of the aforementioned aminopolycarboxylic acids. Suitable organic sequestrants are additionally polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers. The term "acrylic acid homopolymer" also comprises polymers in which some or all of the carboxylic acid groups are present in neutralized form. Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids. Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C4-C8-dicarboxylic acids. Suitable unsaturated C4-C8-dicarboxylic acids in this context are, for example, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, methylenemalonic acid and citraconic acid. Suitable polymeric compounds containing carboxylic acid groups are also homopolymers of the monoethylenically unsaturated Cs-Cs-monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, 2-phenylacrylic acid, cinnamic acid, vinylacetic acid and sorbic acid, copolymers of dicarboxylic acids, for example of maleic acid and acrylic acid; terpolymers of maleic acid, acrylic acid and a vinyl ester of a Ci-Cs-carboxylic acid; and copolymers of maleic acid with C2-Cs-olefins.

[0260] If present, sequestrants are preferably present in amounts of 0.5 % to 50 wt.-%, more preferably 5 to 25 wt.-%, based on the total weight of the composition.

[0261] Suitable enzymes are those typically used in laundry, dishwashing or cleaning compositions. Enzyme herein means catalytically active proteins which are characterized by an amino acid sequence. Variants of an enzyme may be described by a certain sequence identity of an amino acid sequence of the variant when compared to a respective starting sequence. For calculation of sequence identities, in a first step a pairwise global sequence alignment has to be produced, meaning that two sequences have to be aligned over their complete length typically by using the algorithm of Needleman and Wunsch (J. Mol. Biol. (1979) 48, p. 443-453). Preferably, the program “NEEDLE” (The European Molecular Biology Open Software Suite (EMBOSS)) is used for the purposes of the current invention, with using the programs default parameter (gap open=10.0, gap extend=0.5 and matrix=EBLOSUM62). In a second step, % identity is calculated: Coidentity = (identical residues I length of the alignment region which is showing the respective sequence of this invention over its complete length) *100.

[0262] The enzymes are preferably selected from hydrolases, such as proteases, esterases, glucosidases, lipases, DNAses, amylases, cellulases, mannanases, other glycosylhydrolases and mixtures of the aforementioned enzymes. All these hydrolases contribute to dissolution and removal of soil from protein-, grease- or starch-containing stains / resi- dues. For bleaching, it is also possible to use oxidoreductases. Particularly suitable are active enzymatic ingredients obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.

[0263] Suitable enzyme stabilizers are for example calcium propionate, sodium formate, boric acid or salts thereof, boronic acids and salts thereof, polyols, peptide aldehydes, and / or antioxidants. Suitable boronic acids are for examples aromatic and heteroaromatic boronic acids, such as benzene boronic acid (BBA; also termed phenylboronic acid (PBA)), 4-formylphenylboronic acid (4-FPBA), 2-FPBA, 3-FPBA, 4-carboxyphenyl- boronic acid (4-CPBA), 4-(hydroxymethyl)-phenylboronic acid (4-HMPBA), p-tol- ylboronic acid (p-TBA), to name just a few. Suitable polyols are for example polyols containing from 2 to 6 hydroxyl groups, such as ethylene glycol, propylene glycol, 1 ,2- propanediol, 1 ,2-butanediol, 1 ,2-pentanediol, hexyleneglycol, glycerol, sorbitol, mannitol, erythriol, glucose, fructose, and lactose. Peptide aldehydes are oligopeptides with reduced C-terminus (i.e. in which the C(O)OH group is reduced to an aldehyde [CH(O)] group) Suitable peptide aldehydes are for example di-, tri- or tetrapeptide aldehydes and aldehyde analogues (either of the form B1-BO-R wherein, R is H, CH3, CX3, CHX2, or CH2X (where X = halogen), BO is a single amino acid residue including such with an optionally substituted aliphatic or aromatic side chain; and B1stands for one or more (e.g. 1 , 2 or 3) amino acid(s), optionally comprising an N-terminal protection group, or is a protease inhibitor of the protein type such as RASI, BASI, WASI (bifunctional alpha-amylase / subtilisin inhibitors of rice, barley and wheat) or CI2 or SSI. Hydrotropic agents are compounds which solubilizes hydrophobic compounds in aqueous solution by means other than micellar solubilization. Similar to surfactants, hydrotropes often (but not necessarily) consist of a hydrophilic part and a hydrophobic part, but in contrast to surfactants the hydrophobic part is generally too small to cause spontaneous self-aggregation. Examples are aromatic sulfonic acid salts, such as the alkali metal, earth alkaline metal or ammonium salts of p-toluenesulfonic acid (e.g. sodium, potassium, calcium or ammonium p-tosylate), of xylene sulfonic acids (e.g. the sodium, potassium, calcium or ammonium salts of o-, m- or p-xylene sulfonates) or of cumene sulfonic acids, generally of p-cumene sulfonic acid (e.g. the sodium, potassium, calcium or ammonium salts of p-cumenesulfonate); adenosine triphosphate (ATP); and urea.

[0264] A suitable bleaching agent is hydrogen peroxide. Moreover, some enzymes have bleaching properties.

[0265] Dyes can be added to obtain a specific aesthetic appearance, but also be used as shading dyes for reducing or avoiding (auto-)oxidation of components of the composition, especially of unsaturated organic compounds, triggered by UV or visible light (e.g. if the container in which the composition is kept allows transmission of UV or visible light) and / or transition metal ion catalysis (if present). If used as shading dyes, these impart generally a violet or blue color. Shading dyes are particularly useful in laundry compositions, such as laundry detergents or textile softening compositions, where they can help avoiding yellowing of the textiles.

[0266] Examples for shading dyes are direct dyes (also known as substantive dyes; water soluble dyes with an affinity for fibres and which are taken up directly; generally azo dyes), e.g. violet 7, direct violet 9, direct violet 11 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , and direct violet 99; moreover direct violet 66; acid dyes, such as azine dyes, e.g. acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98; or non-azine dyes, e.g. acid violet 17, acid black 1 and acid blue 29; hydrophobic dyes (dyes which do not contain any charged water solubilising group; generally selected from the groups of disperse and solvent dyes, in particular blue and violet anthraquinone and mono-azo dyes, e.g. solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77; basic dyes (organic dyes which carry a net positive charge and deposit onto cotton), e.g. triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 ; reactive dyes (dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond, and deposit onto cotton), e.g. reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96; and dye conjugates (formed by binding direct, acid or basic dyes to polymers or particles via physical forces).

[0267] Suitable pigments can be inorganic (e.g. iron oxide, titan oxide, iron hexacyanoferrate) or organic (e.g. alizarin-, azo- and phthalocyanine colorants).

[0268] Depending on the desired pH, pH adjusting agents (= pH modifiers) are acids, bases and also buffers.

[0269] The acids can be inorganic or organic. Suitable inorganic acids are for example sulfuric acid, hydrochloric acid and phosphoric acid. Suitable organic acids are for example aliphatic, saturated non-substituted Ci-Ce-mono-, di- and tri-carboxylic acids such as formic acid, acetic acid, propanoic acid, oxalic acid, succinic acid and glutaric acid; aliphatic, saturated Ci-Ce-mono-, di- and tri-carboxylic acids carrying one or more OH groups, such as lactic acid, tartric acid and citric acid; aliphatic, unsaturated Ci-Ce- mono-, di- and tri-carboxylic acids such as sorbic acid; aromatic carboxylic acids, such as benzoic acid, salicylic acid and mandelic acid, and sulfonic acids, such as methanesulfonic acid or toluenesulfonic acid. Suitable bases are in particular inorganic bases, such as the carbonates mentioned in context with the sequestrant, e.g. sodium or potassium carbonate; further alkali metal and earth alkaline meal hydroxides, such as NaOH or KOH. Suitable buffering agents are the typical systems, such as hy- drogenphosphate / dihydrogenphosphate buffer, carbonate / hydrogencarbonate buffer, acetic acid / acetate buffer or T ris buffer. Moreover, most of the above acids which are weak and the anion of which is not a strong salt also have buffering capacity.

[0270] Pearlescent agents and opacifiers serve for aesthetic purposes and are to provide a pearlescent or opalescent appearance to the composition. Generally, they are insoluble solids which are in a fine state of subdivision. Examples for inorganic pearlescent agents or opacifiers are inorganic natural substances, such as mica, bismuth oxychloride and titanium dioxide; examples for organic pearlescent agents or opacifiers are fish scales, metal salts of higher fatty acids, fatty glycol esters and fatty acid alkanolamides.

[0271] Viscosity modifiers (rheology modifiers), in this context generally thickeners, serve to impart the desired viscosity to the composition of the invention. Any known thickener is suitable in principle, provided that it does not exert any adverse effect on the efficacy of the composition. Suitable thickeners may either be of natural origin or of synthetic nature. Thickeners of natural origin are mostly derived from polysaccharides. Examples are xanthan, gellan gum, carob flour, guar flour or gum, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins, pectins and cellulose derivatives, such as carboxymethylcellulose, hydroxyethylcellulose, hydrophobically modified hydroxyethyl cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose and the like. Thickeners of natural origin are also inorganic thickeners, such as polysilicic acids and clay minerals, for example sheet silicates, and also the silicates mentioned for the builders. More specific examples are listed in the following table. Most are derived from smectite clays and silica derivatives.

[0272] Examples of synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partly) crosslinked homopolymers of acrylic acid, for example homopolymers of acrylic acid which have been crosslinked with an allyl ether of sucrose or pentaerythritol, or with propylene (carbomers), for example the Carbopol® brands from BF Goodrich (e.g. Carbopol® 676, 940, 941 , 934 and the like) or the Polygel® brands from 3V Sigma (e.g. Polygel® DA), copolymers of ethylenically unsaturated mono- or dicarboxylic acids, for example terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl acrylate or ethyl acrylate and a (meth)acrylate which derives from long- chain ethoxylated alcohols, for example the Acusol® brands from Rohm & Haas (e.g. Acusol® 820 or 1206A), copolymers of two or more monomers which are selected from acrylic acid, methacrylic acid and the Ci-C4-alkyl esters thereof, for example copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl methacrylate, for example the Aculyn® and Acusol® brands from Rohm & Haas (e.g. Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers, for example copolymers of C -Cso-alkyl acrylates with one or more comonomers selected from acrylic acid, methacrylic acid and the Ci-C4-alkyl esters thereof, said copolymers having been crosslinked with an allyl ether of sucrose or pentaerythritol (e.g. Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas). Suitable thickeners are moreover phospholipids, such as alkylated phosphatidyl choline, phosphobetaines or alkyl phosphate quaternary compounds; reaction products of maleic acid polymers with ethoxylated long-chain alcohols, for example the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP; polyethylene glycols, polyamides, polyimines and polycarboxylic acids; dibenzylidene polyol acetal derivatives (DBPA derivative); these may comprise a dibenzylidene sorbitol acetal derivative (DBS); di-amido gellants; non-poly- meric crystalline, hydroxyl functional structurants which comprise a crystallizable glyceride, to name just a few.

[0273] Suitable inorganic salts are for example sodium chloride and calcium chloride. The compounds and compositions of the invention find particular use as surfactants in detergents, specifically laundry detergents and manual dishwashing products. These are generally comprised of a number of components besides the compound(s) (I. a) and / or (l.b). The composition typically comprises a total amount of 0.1 to 15 wt.-% of the com- pound(s) (I. a) and / or (l.b), relative to the weight of the composition. Typical compositions are known to the experts.

[0274] Laundry detergents typically comprise other surfactants of the anionic, nonionic, amphoteric or cationic type; builders such as phosphates, aminocarboxylates and zeolites; organic co-builders such as polycarboxylates; bleaching agents and their activators; foam controlling agents; enzymes; anti-greying agents; optical brighteners; and stabilizers.

[0275] Liquid laundry detergents generally comprise the same components as granular laundry detergents, but generally contain less of the builders. Moreover, liquid detergent formulations often comprise hydrotropic substances. All-purpose cleaning agents may comprise other surfactants, builders, foam suppressing agents, hydrotropes and solubilizer alcohols.

[0276] Builders may be comprised in amounts of up to 90% by weight, preferably about 5 to 35% by weight, to intensify the cleaning action. Examples of common inorganic builders are phosphates, polyphosphates, alkali metal carbonates, silicates and sulfates. Examples of organic builders are polycarboxylates, aminocarboxylates such as ethylenediaminetetraacetates, nitrilotriacetates, hydroxycarboxylates, citrates, succinates and substituted and unsubstituted alkanedi- and polycarboxylic acids.

[0277] Another type of builder, useful in granular laundry and built liquid laundry agents, includes various substantially water-insoluble materials which are capable of reducing the water hardness, e.g., by ion exchange processes. In particular, complex sodium aluminosilicates, known as type A zeolites, are useful for this purpose.

[0278] The laundry detergents may also contain bleaching agents, e.g., percompounds such as perborates, percarbonates, persulfates and organic peroxy acids. Formulations containing percompounds may also contain stabilizing agents, such as magnesium silicate, sodium ethylenediaminetetraacetate or sodium salts of phosphonic acids. In addition, bleach activators can be used to increase the efficiency of the inorganic persalts at lower washing temperatures. Particularly useful for this purpose are substituted carboxylic acid amides, e.g., tetraacetylethylenediamine, substituted carboxylic acids, e.g., isononyloxybenzenesulfonate and sodium cyanamide.

[0279] Examples of suitable hydrotropic substances are alkali metal salts of benzene, toluene and xylene sulfonic acids; alkali metal salts of formic acid, citric and succinic acid, urea, mono-, di-, and triethanolamine. Examples of solubilizer alcohols are ethanol, isopropanol, mono- or polyethylene glycols, monopropylene glycol and ether alcohols.

[0280] Examples of foam controlling agents are high molecular weight fatty acid soaps, paraffinic hydrocarbons, and silicon containing defoamers. In particular, hydrophobic silica particles having silicon adsorbed thereon are efficient foam control agents in these laundry detergent formulations.

[0281] Examples of known enzymes which are effective in laundry detergent agents are, among others, proteases, amylases, cellulases, mannanases, and lipases. Preference is given to enzymes which have their optimum performance at the design conditions of the detergent.

[0282] A large number of fluorescent Whiteners are described in the literature. For laundry detergent formulations, the derivatives of diaminostilbene disulfonates and substituted distyrylbiphenyl are particularly suitable.

[0283] As anti-greying agents, water-soluble colloids of an organic nature are preferably used. Examples are water-soluble polyanionic polymers such as polymers and copolymers of acrylic and maleic acid, cellulose derivatives such as carboxymethyl cellulose, methyl- and hydroxyethylcellulose.

[0284] In addition to one or more of the aforementioned other surfactants and other detergent composition components, laundry detergent compositions typically comprise one or more inert components. For instance, the balance of liquid detergent composition is typically an inert solvent or diluent, most commonly water.

[0285] Manual dishwashing products may comprise, besides the compounds obtained in the process of the invention, other surfactants of the anionic, nonionic, amphoteric or cationic type; solvents; diamines; carboxylic acids or salts thereof; polymeric suds stabilizers; enzymes; builders; perfumes; and / or chelating agents.

[0286] Suitable solvents include diols, polymeric glycols, and mixtures thereof. Preferred diols include propylene glycol, 1 ,2 hexanediol, 2-ethyl-1 ,3-hexanediol and 2,2,4-trimethyl-1 ,3- pentanediol.

[0287] Polymeric glycols, which comprise ethylene oxide (EO) and propylene oxide (PO) groups, may also be included in the present invention. These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains. A preferred polymeric glycol is a polypropylene glycol having an average molecular weight in the range of 1 ,000 to 5,000 g / mol. When polymeric glycols are present, it may be beneficial to include either a diol and / or an alkali metal inorganic salt, such as sodium chloride, so as to obtain satisfactory physical stability. Suitable amounts of diols to provide physical stability are in the amounts in the ranges found above.

[0288] Further suitable solvents include glycols or alkoxylated glycols, ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, aromatic alcohols, alkoxylated aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, linear C1-C5 alcohols, alkoxylated linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halo hydrocarbons, Ce-Cie glycol ethers, and mixtures thereof.

[0289] Suitable alkoxylated glycols are methoxy octadecanol and / or ethoxyethoxyethanol. Suitable aromatic alcohols include benzyl alcohol. Suitable aliphatic branched alcohols include 2-ethylbutanol and / or 2-methylbutanol. Suitable alkoxylated aliphatic branched alcohols include 1 -methylpropoxyethanol and / or 2-methylbutoxyethanol. Suitable linear C1-C5 alcohols include methanol, ethanol, and / or propanol.

[0290] Manual dishwashing compositions typically comprise 0.01 to 20 wt.-% of solvent, based on the total weight of the composition. The solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present.

[0291] Manual dishwashing compositions may further comprise one or more diamines.

[0292] The composition preferably comprises 0.1 to 15 wt.-% of at least one diamine, based on the total weight of the composition.

[0293] Suitable diamines include organic diamines in which pK1 and pK2 are in the range of 8.0 to 11.5, such as 1 ,3-bis(methylamine)-cyclohexane (pKa = 10 to 10.5), 1 ,3-propane diamine (pK1=10.5; pK2=8.8), 1 ,6-hexane diamine (pK1 = 11 ; pK2 = 10), 1 ,3-pentane diamine (pK1 = 10.5; pK2 = 8.9), 2-methyl-1 ,5-pentane diamine (Dytek A) (pK1 = 11.2; pK2 = 10.0). pKa values referenced herein may be obtained from literature, such as from "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, NY and London, 1975. The pKa of the diamines is specified in an all-aqueous solution at 25°C and for an ionic strength between 0.1 to 0.5 M.

[0294] Other preferred materials are primary diamines having two primary amino groups with alkylene spacers ranging from C4 to Cs.

[0295] The compositions according to the present invention may comprise a linear or cyclic carboxylic acid or salt thereof. Where the acid or salt thereof is present and is linear, it preferably comprises from 1 to 6 carbon atoms whereas where the acid is cyclic, it preferably comprises greater than 3 carbon atoms. The linear or cyclic carbon-containing chain of the carboxylic acid or salt thereof may be substituted with a substituent group selected from the group consisting of hydroxyl, ester, ether, aliphatic groups having from 1 to 6, more preferably 1 to 4 carbon atoms and mixtures thereof.

[0296] Preferred carboxylic acids are those selected from the group consisting of salicylic acid, maleic acid, acetyl salicylic acid, 3-methyl salicylic acid, 4-hydroxy isophthalic acid, dihydroxyfumaric acid, 1 ,2,4-benzene tricarboxylic acid, pentanoic acid and salts thereof and mixtures thereof. Where the carboxylic acid exists in the salt form, the cation of the salt is preferably selected from alkali metal, alkaline earth metal, monoethanolamine, diethanolamine or triethanolamine and mixtures thereof.

[0297] The carboxylic acid or salt thereof is preferably present in an amount from 0.1% to 5 wt.-%, based on the total weight of the composition.

[0298] The composition may comprise a polymeric suds stabilizer. These polymeric suds stabilizers provide extended suds volume and suds duration without sacrificing the grease cutting ability of the liquid detergent compositions. Suitable polymeric suds stabilizers include homopolymers of (N,N-di(Ci-Cs alkyl)amino)(Ci-C8)alkyl acrylate esters; and copolymers thereof.

[0299] The molecular weight of the polymeric suds stabilizers is preferably in the range of 1 ,000 to 2,000,000 g / mol, most preferably from 20,000 to 500,000 g / mol. Polymeric suds stabilizer may be present in the form of a salt, for example the citrate, sulfate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester. One preferred polymeric suds stabilizer is (N,N-dimethylamino)alkyl acrylate ester. Polymeric suds stabilizers are preferably present in an amount of 0.01 % to 15 wt.-%, based on the total weight of the composition.

[0300] Suitable builders include aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylene-diamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylene-phosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used.

[0301] Suitable polycarboxylate builders include citric acid, preferably in the form of a water- soluble salt, and derivatives of succinic acid. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts. Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid, as described in US 4,663,071.

[0302] Suitable fatty acid builders include saturated and unsaturated C10-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.

[0303] Builders are preferably present in amounts of 0.5 % to 50 wt.-%, more preferably 5 to 25 wt.-%, based on the total weight of the composition.

[0304] Suitable enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, p-glucanases, arabinosidases or mixtures thereof. Enzymes may be present in amounts of 0.0001 % to 5 wt.-% of active enzyme, based on the total weight of the composition.

[0305] Preferred proteolytic enzymes, then, are selected from the group consisting of Alcalase® (Novo Industri A / S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred. Preferred amylase enzymes include TERMAMYL®, DU- RAMYL® and the amylase enzymes those described in WO 9418314 to Genencor International and WO 9402597 to Novo.

[0306] Suitable chelating agents include iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phos- phonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Suitable amino carboxylates include ethylenediaminetetraacetates, N-hydroxyethyleth- ylenediaminetriacetates, nitrilo-tri-acetates, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof. Suitable amino phosphonates include ethylenediaminetetrakis (methylenephospho- nates). Suitable polyfunctionally-substituted aromatic chelating agents include dihy- droxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene.

[0307] Chelating agents may be present in amounts of 0.00015% to 15 wt.-%, based on the weight of the composition. to the invention

[0308] The present invention relates moreover to a compound of the formula (I. a) or of the formula (l.b) as defined above, except for following compounds:

[0309] - compounds (l.b) wherein R1ais OH or oxo, R2aand R3aare hydrogen, Y is -OR6and R6is dodecyl;

[0310] - compound (l.b) wherein R1ais oxo, R2aand R3aare hydrogen, Y is -OR6and R6is n- hexyl;

[0311] - compound (l.b) wherein R1ais OH, R2aand R3aare hydrogen, Y is -NR7R8, R7is n- hexadecyl and R8is hydrogen.

[0312] As far as applicable, the above remarks, explanations and preferred embodiments mentioned above for compounds (I. a) and (l.b) in context with the use according to the invention apply here analogously.

[0313] In an embodiment, the compound of the formula (l.b) is not a C6-Ci2-alkylester of shi- kimic acid, a C6-Ci2-alkylesters of 3-dehydroshikimic acid, N-hexadecyl shikimic acid amide or N-tridecyl shikimic acid amide.

[0314] In an embodiment, in compounds of the formula (l.b) at least one of R1bb, R2band R3bis a group -S(O)3H or -S(O)3'M+.

[0315] Preferably, in compounds (I. a)

[0316] R1ais oxo and at least one of R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3'M+; or R1ais OR1aaand at least one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3-M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3'M.

[0317] More preferably, in compounds (I. a)

[0318] R1ais oxo and on average one of R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+; and the other three of R2a, R3a, R4and R5are hydrogen, or R1ais OR1aaand on average one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+; and the other four of R1aa, R2a, R3a, R4and R5are hydrogen.

[0319] As explained above, “on average” means to express that not all compounds (I. a) contain exactly one group -S(O)3H or -S(O)3'M+. A part of the compounds (I. a) may for instance contain two groups -S(O)3H or -S(O)3'M+and a part no such groups. Compounds (I. a) wherein on average one of one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+are obtainable in technical processes, e.g. by reacting a compound (I. a) wherein all of R1aa, R2a, R3a, R4and R5are hydrogen with a sulfonation agent. The resulting product is principally a compound (I. a) wherein exactly one of one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+; but depending on the reaction conditions, the product may also contain minor amounts of compounds (I. a) wherein for instance two and none of one of R1aa, R2a, R3a, R4and R5are a group -S(O)3H or -S(O)3'M+. Compounds (l.b) wherein exactly one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+may be isolated from such mixtures, but for the purpose of the present invention this is not necessary, and such mixtures are useful as well. Generally, the amount of compounds (I. a) wherein two and none of R1aa, R2a, R3a, R4and R5are a group -S(O)3H or -S(O)3'M+is not large anyway.

[0320] In particular, in compounds (I. a) one of R4and R5is -S(O)3'M+and the other of R4and R5is hydrogen; R2aand R3aare hydrogen; and R1ais oxo or OR1aa, wherein R1aais hydrogen.

[0321] More particularly, in compounds (I. a) one of R4and R5is -S(O)3'M+and the other of R4and R5is hydrogen; R2aand R3aare hydrogen; and R1ais OR1aa, wherein R1aais hydrogen.

[0322] Due to the preparation method preferably applied for preparing compounds (I. a) (see below), among R4and R5, the -S(O)3H or -S(O)3'M+group is preferably in the position of R5, and R4is thus preferably hydrogen.

[0323] Preferably in compounds (l.b)

[0324] R1bis oxo and R2band R3bare hydrogen; or R1bis OH and R2band R3bare hydrogen.

[0325] More preferably, in compounds (l.b)

[0326] R1bis oxo and R2band R3bare hydrogen; or R1bis OH and R2band R3bare hydrogen.

[0327] More preferably, in compounds (l.b) R1bis OH and R2band R3bare hydrogen.

[0328] Among compounds (la.) and (l.b), preference is given to compounds (I. a).

[0329] In view of their use as surfactants, in compounds (I. a) and (l.b), among groups -S(O)3H and -S(O)3'M+preference is given to group -S(O)3'M+. Preferably, the compound of the formula (I. a) is a compound of the formula (l.a.1), (I. a.2) or (I. a.3), and the compound of the formula (l.b) is a compound of the formula (l.b.1), (l.b.2) or (l.b.3):

[0330] Preferably, M+is an alkali metal cation or an alkaline earth metal cation equivalent, more preferably Na+, K+, (Mg2+)i / 2 or (Ca2+)i / 2, in particular Na+or K+, and is specifically Na+.

[0331] In a preferred embodiment, Y in compounds (I. a) and (l.b) is -OR6.

[0332] In another preferred embodiment, Y in compounds (I. a) and (l.b) is -NR7R8.

[0333] More preference is however given to Y being -OR6.

[0334] R6and R7, independently of each other, are preferably Cs-Cso-alkyl, more preferably Cio-Ci8-alkyl, even more preferably Cio-Ci4-alkyl, and specifically n-dodecyl. R8is preferably hydrogen.

[0335] Since it is desired to provide surfactants which are obtained at least partly from renewable sources, especially from bio-based sources, it is preferred that Y be derived from such a source. The group OR6is for example derived from an alcohol R6OH. Renewable, to be more precise bio-based sources for such alcohols are for example fats and oils of animal or vegetal origin, which triglycerides can be hydrolized and the resulting fatty acids reduced to fatty alcohols. The fatty acids can alternatively be converted into fatty amines. Most fatty acids obtained from natural oils and fats contain an linear alkyl or alkenyl chains.

[0336] Moreover, linear alkyl or alkenyl chains are generally better biodegradable than branched residues.

[0337] Accordingly, in a preferred embodiment, R6and R7, independently of each other, are linear Cs-Cso-alkyl, more preferably linear C -Cis-alkyl, and in particular linear C10-C14- alkyl.

[0338] Most alkyl or alkenyl chains contained in fatty acids obtained from natural oils and fats are of an even carbon number.

[0339] Moreover alkyl or alkenyl chains with an even carbon number are generally better biodegradable than alkyl or alkenyl chains with an odd carbon number.

[0340] Accordingly, in a preferred embodiment, R6and R7, independently of each other, are linear Cs-Cso-alkyl with an even carbon number, more preferably linear Cw-Cis-alkyl with an even carbon number, and in particular linear C -Ci4-alkyl with an even carbon number.

[0341] In particular, R6and R7, independently of each other, are n-decyl, n-dodecyl, n- tetradecyl, n-hexadecyl or n-octadecyl, and more particularly n-decyl, n-dodecyl or n- tetradecyl. Specifically, R6and R7, independently of each other, are n-dodecyl.

[0342] In each case, R8is preferably hydrogen.

[0343] As said, it is desired to provide surfactants which are obtained at least partly from renewable sources, especially from bio-based sources. Renewable sources have been described above.

[0344] In a preferred embodiment, at least a part of the compounds (I. a) and (l.b) is derived from gallic acid, shikimic acid or 3-dehydroshikimic acid which are obtained from a renewable, preferably bio-based, source and / or is derived from an alcohols R6OH or an amine NHR7R8which is obtained from a renewable, preferably bio-based, source. More preferably in the compounds (I. a) and (l.b) at least 20 mol-%, in particular at least 30 mol-%, especially at least 50 mol% or up to 100 mol-% of the carbon atoms, relative to the total amount of carbon atoms in the compounds (I. a) and (l.b), stem from a renewable source. Even more preferably, in the compounds (I. a) and (l.b) at least 20 mol-%, in particular at least 30 mol-%, especially at least 50 mol% or up to 100 mol-% of the carbon atoms, relative to the total amount of carbon atoms in the compounds (I. a) and (l.b), are bio-based.

[0345] Method for preparing compounds (I. a)

[0346] The present invention relates further to a method for preparing a compound (I. a) wherein one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other of R4and R5is hydrogen, comprising

[0347] (i.1) reacting a compound (II) where Y is as defined above and R1ais oxo or OR1aa, where R1aais hydrogen, with a sulfonation agent; and

[0348] (ii.1) if desired (and if at all necessary; see below remarks) reacting the compound (I. a) obtained in step (i.1) with a base to obtain a compound (I. a) wherein one of R4and R5is a group -S(O)3'M+and the other of R4and R5is hydrogen, and where optionally also one of R1aa(if present) R2aand R3ais a group -S(O)3'M+.

[0349] Suitable sulfonation agents are known in the art, preference being given to hydrogensulfites, chlorosulfonic acid (CISO3H), sulfur trioxide (SO3), mixtures of sulfur trioxide (SO3) and air; sulfamic acid and oleum (fuming sulfuric acid; sulfuric acid with excess sulfur trioxide). Sulfur trioxide (SO3), mixtures thereof with air and sulfamic acid are rather suitable on an industrial scale, whereas alkali metal or ammonium hydrogensulfites, chlorosulfonic acid and oleum can also be used on laboratory scale (on industrial scale too, of course).

[0350] Hydrogensulfites are salts of formula M+HSC>3', where M+is an ammonium cation (NHY) or metal cation equivalent. Expediently, M+corresponds to M+in the group -S(O)3'M+to be present in the compound (I. a). Preferably, M+is an ammonium cation (NHY) or an alkali metal cation. Suitable alkali metal hydrogensulfites are the lithium, sodium or potassium hydrogensulfite. Among alkali metal and ammonium hydrogensulfites, preference is given to sodium or potassium hydrogensulfite, more preference to sodium hydrogensulfite (Na+HSC>3').

[0351] Compound (II) and the sulfonation agent are preferably used in a molar ratio of 3:1 to 1 :4, more preferably 1.5:1 to 1 :3, in particular 1 :1 to 1 :3 and specifically 1 :1 to 1 :2.5, e.g. 1 :1.5 to 1 :2.5. In case of mixtures of sulfur trioxide (SO3) and air, the molar amount refers to the amount of sulfur trioxide contained in these mixtures. In case of oleum, the molar amount refers to the amount of sulfur trioxide contained therein.

[0352] The reaction in step (ii.a) can be carried out in substance (neat) or in a solvent. Suitable solvents are those which are inert (and especially do not react with the sulfonation agent) and do not interfere negatively with the reaction. Examples are alkanes, such as pentane, hexane, heptane, octane or petroleum ether; halogenated alkanes, such as dichloromethane or trichloromethane; cycloalkanes, such as cyclohexane or cycloheptane, acyclic ethers, such as diethyl ether, dipropyl ether, diisopropyl ether or methyl- tert-butyl ether; cyclic ethers, such as tetrahydrofuran, 2-methyltetrahydrofuran or 1 ,4- dioxane, or carboxamides, such as N,N-dimethylformamide or N,N-dimethylacetamide.

[0353] In case that a reactive sulfonation agent, such as chlorosulfonic acid, sulfur trioxide, mixtures of sulfur trioxide and air, sulfamic acid or oleum is used, to prevent reaction with the sulfonation agent, the solvent is preferably anhydrous.

[0354] Hydrogensulfites, by contrast, are not impaired by water, so that the solvent need not be anhydrous and may even contain substantial amounts of water. If such aqueous mixtures are used, the organic solvent is preferably water-miscible. Thus, in this case, among the above-listed solvents, preference is given to the cyclic ethers (such as tetrahydrofuran, 2-methyltetrahydrofuran or 1 ,4-dioxane) and the carboxamides (such as N,N-dimethylformamide or N,N-dimethylacetamide). Moreover, Ci-Cs-alkanols (i.e. methanol, ethanol, n-propanol or isopropanol) are suitable as such or in admixture with water. If mixtures of organic solvents with water are used, these may contain up to 60% by weight of water, e.g. 10 to 60 or 20 to 60% by weight, preferably up to 50% by weight, e.g. 10 to 50 or 20 to 50% by weight, relative to the total weight of organic solvent and water.

[0355] Among the above sulfonation agents, preference is given to hydrogensulfites, in particular to ammonium or alkali metal hydrogensulfites, specifically to sodium or potassium hydrogensulfite, very specifically to sodium hydrogensulfite.

[0356] The reaction is preferably carried out at a temperature in the range of from -20 to 120°C, preferably from -10 to 100°C, e.g. from 0 to 95°C. In case of the use of reactive sulfonation agents, such as chlorosulfonic acid, sulfur trioxide, mixtures of sulfur trioxide and air, sulfamic acid or oleum, the reaction is more preferably carried out at a temperature in the range of from -20 to 10°C, in particular from -10 to 25°C, e.g. from 0 to 20°C.

[0357] In case of the use of an alkali metal or ammonium hydrogensulfite, the reaction is more preferably carried out at a temperature in the range of from 20 to 120°C, in particular from 50 to 100°C and specifically from 70 to 100°C, e.g. from 80 to 95°C.

[0358] In case of using sulfur trioxide and air as sulfonation agent, it has proved advantageous to use a falling film apparatus. In this set-up, the compound (l.b) is expediently liquefied or dissolved in a solvent. The liquefied or dissolved reactant runs through a vertical tube at its surface. Gaseous sulfur trioxide in air with reduced content of oxygen (preferably <16 vol-%, more preferably <12 vol-%, relative to the total volume of the sulfur trioxide / air mixture) is injected through the tube as well. The resulting sulfuric acid compound can, if desired, be afterwards neutralized with a base, as described below for step (ii.1).

[0359] Without wishing to be bound by theory, it is assumed that the reaction takes place in a conjugated, Michael-type addition reaction when a hydrogensulfite is used as sulfonation agent, affording a compound (I. a) wherein R5is preferably a group -S(O)3H or -S(O)3'M+and R4is preferably hydrogen.

[0360] Depending on the sulfonation agent and also on the amount in which this is used, a part of the OH groups may also be sulfated.

[0361] If an alkali metal or ammonium hydrogensulfite is used as sulfonation agent, step (i.1 ) affords a compound (I. a) wherein one of R4and R5(generally R5; see above remarks) is a group -S(O)3H and the other of R4and R5(generally R4) is hydrogen, and where optionally also one of R1aa(if present), R2aand R3ais a group -S(O)3H. Since however hydrogensulfites are no very good sulfation agents, generally only one of R4and R5is -S(O)3H and R1aa(if present), R2aand R3aare hydrogen. Principally, a part of R4and R5(generally R5) (and also of R1aa(if present), R2aand R3a, if applicable) might also be obtained in the salt form -S(O)3'M+, but since step (i.1 ) is preferably carried out at an acidic pH (in the case of the use of hydrogensulfites preferably at a pH of at most 6, more preferably at most 5), the salt form is not obtained directly in the sulfonation step. To convert the group(s) -S(O)3H into -S(O)3'M+group(s), step (ii.1 ) is thus generally necessary.

[0362] If chlorosulfonic acid (CISO3H) is used as sulfonation agent, R4or R5in the resulting product is generally a sulfonylchloride group (-S(=O)2CI). This is converted into a compound (I. a) wherein one of R4and R5is a group -S(O)3H (and wherein optionally also one of R1aa(if present), R2aand R3ais a group -S(O)3H) by hydrolysis with water. If a compound (I. a) is desired wherein one of R4and R5is a group -S(O)3'M+(and optionally one of R1aa(if present), R2aand R3ais also a group -S(O)3'M+), this can alternatively be obtained from the sulfonylchloride by direct reaction with a base (to avoid high ex- othermy, it is however preferred to first hydrolyze the sulfonylchloride compound with water and react the resulting sulfonic acid with a base).

[0363] If sulfur trioxide, a mixture of sulfur trioxide and air, sulfamic acid or oleum is used as sulfonation agent, step (i.1) affords a compound (I. a) wherein one of R4and R5is a group -S(O)3H and the other of R4and R5is hydrogen, and where optionally also one of R1aa(if present), R2aand R3ais a group -S(O)3H.

[0364] In step (ii.1) a part or, preferably, all -S(O)3H groups (or a part or, preferably, all -S(O)3CI groups, if these are converted directly without intermediate hydrolysis to -S(O)3H) in compounds (I. a) are converted into -S(O)3'M+groups.

[0365] Suitable bases for step (ii.1) are the hydroxides, carbonates or hydrogencarbonates of the desired metal M, preference being given to alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogencarbonates, and alkaline earth metal hydrogencarbonates, more preference being given to alkali metal hydroxides and alkaline earth metal hydroxides, even more preference to alkali metal hydroxides, and in particular to NaOH or KOH.

[0366] The bases are generally used in aqueous solution.

[0367] The base is preferably used in an amount to convert all -S(O)3H groups (or all -S(O)3CI groups, if these are converted directly without intermediate hydrolysis to -S(O)3H) into -S(O)3'M+groups. The base is thus preferably used in equimolar amount or in slight excess. In case of hydroxides, these are preferably used in such an amount that the molar ratio of compound (II) to the hydroxide base is 1 :1 to 1 :2, more preferably 1 :1.1 to 1 :1.6 or 1 :1.2 to 1 :1.6 (the amount of hydroxide bases relates to the hydroxide anions contained therein; thus in case of alkaline earth metal hydroxides the molar ratio of compound (II) to the alkaline earth metal hydroxide M(OH)2 is preferably 1 :0.5 to 1 :1 , more preferably 1 :0.55 to 1 :0.8 or 1 :0.6 to 1 :0.8, since 1 mol of M(OH)2 contains 2 mol of OH'). If weaker bases are used, such as carbonates or hydrogencarbonates, the base is preferably used in an amount to result in a pH of at least 6.5, e.g. from 6.5 to 9 or 6.5 to 8; more preferably of at least 7, e.g. from 7 to 9 or 7 to 8.

[0368] The target compound (I. a) can be isolated by usual means. If (I. a) is a sulfonic acid, this is for example isolated from the organic phase by removal of the solvent, which is generally carried out distillatively often under reduced pressure. Further purification can be carried out by usual means, e.g. by extractive or chromatographic methods.

[0369] If (I. a) is a sulfonic acid salt, this is for example isolated from the aqueous phase by crystallization. It is however possible to use the compound as aqueous solution without further isolation.

[0370] Compounds (II) wherein R1ais OH are for example obtainable by esterification (with the alcohol R6OH) or amidation (with the amine NHR7R8) of shikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride. The amide (II) (Y = -NR7R8) can also be obtained by amidation of a shikimic acid ester, preferably an ester of a short-chained alkanol, e.g. of the methyl or ethyl shikimate.

[0371] Compounds (II) wherein R1bis oxo are for example obtainable by esterification (with the alcohol R6OH) or amidation (with the amine NHR7R8) of 3-dehydroshikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride. The amide (II) (Y = -NR7R8) can also be obtained by amidation of a 3-dehydroshikimic acid ester, preferably an ester of a short-chained alkanol, e.g. of the methyl or ethyl 3-dehydroshikimate.

[0372] Further details to the esterification and amidation reaction are given below.

[0373] The invention relates also to a method for preparing a compound of the formula (I. a), wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3aa group -S(O)3H or -S(0)3'M+, comprising

[0374] (i.2) reacting a compound (III) where Y is as defined above and R1ais oxo or OR1aa, where R1aais hydrogen, with a sulfonation agent to obtain a compound (I. a) wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3ais a group -S(O)3H; and (ii.2) if desired reacting the compound (I. a) obtained in step (i.2) with a base to obtain a compound (I. a) wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3ais a group -S(O)3'M+.

[0375] Suitable sulfonation agents are known in the art, preference being however given to chlorosulfonic acid (CISO3H), sulfur trioxide (SO3), mixtures of sulfur trioxide (SO3) and air; sulfamic acid and oleum (fuming sulfuric acid; sulfuric acid with excess sulfur trioxide). Sulfur trioxide (SO3), mixtures thereof with air and sulfamic acid are rather suitable on an industrial scale, whereas alkali metal or ammonium hydrogensulfites, chlorosulfonic acid and oleum can also be used on laboratory scale (on industrial scale too, of course).

[0376] Otherwise, the above remarks to suitable reaction conditions and neutralization with a base in a step following the sulfatation apply analogously.

[0377] If chlorosulfonic acid, sulfur trioxide, a mixture of sulfur trioxide and air, sulfamic acid or oleum is used as sulfonation agent, step (i.1) affords a compound (I. a) wherein at least one of R1aa(if present), R2aand R3ais a group -S(O)3H (and the others of R1aa(if present), R2aand R3a, if any, are hydrogen.

[0378] In step (ii.2) a part or, preferably, all -S(O)3H groups are converted into -S(O)3'M+groups.

[0379] Suitable bases for step (ii.2) are the hydroxides, carbonates or hydrogencarbonates of the desired metal M, preference being given to alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogencarbonates, and alkaline earth metal hydrogencarbonates, more preference being given to alkali metal hydroxides and alkaline earth metal hydroxides, even more preference to alkali metal hydroxides, and in particular to NaOH or KOH.

[0380] The bases are generally used in aqueous solution.

[0381] The base is preferably used in an amount to convert all -S(O)3H groups into -S(O)3'M+groups. The base is thus preferably used in equimolar amount or in slight excess. In case of hydroxides, these are preferably used in such an amount that the molar ratio of compound (III) to the hydroxide base is 1 :1 to 1 :2, more preferably 1 :1.1 to 1 :1.6 or 1 :1.2 to 1 :1.6 (the amount of hydroxide bases relates to the hydroxide anions contained therein; thus in case of alkaline earth metal hydroxides the molar ratio of compound (II) to the alkaline earth metal hydroxide M(OH)2 is preferably 1 :0.5 to 1 :1 , more preferably 1 :0.55 to 1 :0.8 or 1 :0.6 to 1 :0.8, since 1 mol of M(OH)2 contains 2 mol of OH'). If weaker bases are used, such as carbonates or hydrogencarbonates, the base is preferably used in an amount to result in a pH of at least 6.5, e.g. from 6.5 to 9 or 6.5 to 8; more preferably of at least 7, e.g. from 7 to 9 or 7 to 8.

[0382] The target compound (I. a) can be isolated by usual means. If in (I. a) the sulfate group(s) is / are present in acid form, i.e. as -S(O)3H, compound (I. a) is for example isolated from the organic phase by removal of the solvent, which is generally carried out distillati vely often under reduced pressure. Further purification can be carried out by usual means, e.g. by extractive or chromatographic methods.

[0383] If (I. a) is a sulfate salt, i.e. the sulfate groups are present as S(O)3'M+, compound (I. a) is for example isolated from the aqueous phase by crystallization. It is however possible to use the compound as aqueous solution without further isolation.

[0384] Compounds (III) wherein R1ais OH are for example obtainable by esterification (with the alcohol R6OH) or amidation (with the amine NHR7R8) of gallic acid or a more reactive derivative thereof, such as its acid halide or anhydride, followed by hydrogenation of the phenyl ring. The amide (III) (Y = -NR7R8) can also be obtained by amidation of a gallic acid ester, preferably an ester of a short-chained alkanol, e.g. of the methyl or ethyl gallate, followed by hydrogenation of the phenyl ring.

[0385] Alternatively, compounds (III) wherein R1ais OH are for example obtainable by esterification (with the alcohol R6OH) or amidation (with the amine NHR7R8) of shikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride, followed by hydrogenation of the C-C double bond. The amide (II) (Y = -NR7R8) can also be obtained by amidation of a shikimic acid ester, preferably an ester of a short-chained alkanol, e.g. of the methyl or ethyl shikimate, followed by hydrogenation of the C-C double bond.

[0386] Compounds (I. a) wherein R1ais oxo are for example obtainable by esterification (with the alcohol R6OH) or amidation (with the amine NHR7R8) of 3-dehydroshikimic acid (or a stereoisomer thereof or a mixture of stereoisomers thereof) or a more reactive derivative thereof, such as its acid halide or anhydride, followed by hydrogenation of the C-C double bond. The amide (II) (Y = -NR7R8) can also be obtained by amidation of a 3-de- hydroshikimic acid ester, preferably an ester of a short-chained alkanol, e.g. of the methyl or ethyl 3-dehydroshikimate, followed by hydrogenation of the C-C double bond.

[0387] Esterification of shikimic acid, 3-dehydroshikimic acid or gallic acid to obtain compounds (II) and (III) wherein Y is OR6can be carried out by known means, such as reacting the respective acid (i.e. shikimic acid, 3-dehydroshikimic acid or gallic acid) or a more active derivative thereof, such as an acid halide (e.g. the chloride or bromide), an anhydride or an active ester of the respective acid, with an alcohol with R6OH under typical esterification conditions, if desired under removal of the reaction water formed (if the acid as such is used) or of the acid formed (if an anhydride is used) to enhance the reaction rate, or under neutralization (if an acid halide is used).

[0388] The esterification can be carried out in the presence of an esterification catalyst; this is especially indicated if the acid as such is used. Suitable esterification catalysts are well known in the art and are for example metal based catalysts, e.g. iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts, such as metal alkoxylates; or acids, e.g. mineral acids, such as sulfuric acid, hydrochloric acid or phosphoric acid; organic sulfonic acids, such as methane sulfonic acid or para-toluene sulfonic acid or strongly acidic cation exchange resins.

[0389] The term "strongly acidic cationic exchanger" refers to a cationic exchanger in the H+form which has strongly acidic groups. The strongly acidic groups are generally sulfonic acid groups; they are generally bonded to a polymer matrix, which can be e.g. gel-like and / or macroporous. Preference is given to styrene (co)polymers containing sulfonic acid groups, specifically to styrene-divinyl benzene copolymers containing sul-fonic acid groups. Commercial examples for such cationic exchangers are Lewatit® (Lanxess), Purolite® (The Purolite Company), Dowex® (Dow Chemical Company), Amberlite® (Rohm and Haas Company), Amberlyst® (Rohm and Haas Company). Preferred strongly acidic cation exchangers are: Lewatit® K 1221 , Lewatit® K 1461, Lewatit® K 2431 , Lewatit® K 2620, Lewatit® K 2621 , Lewatit® K 2629, Lewatit® K 2649, Amberlite® FPC 22, Amberlite® FPC 23, Amberlite® IR 120, Amberlyst® 131 , Amberlyst® 15, Amberlyst® 31, Amberlyst® 35, Amberlyst® 36, Amberlyst® 39, Amberlyst® 46, Amberlyst® 70, Purolite® SGC650, Purolite® C1 OOH, Purolite® C 150 H, Dowex® 50X8, Serdolit® red and Nation® NR-50. Alternatively, the cation exchanger can be a perfluorinated ion exchange resin, sold e.g. under the Nation® brand of DuPont.

[0390] The esterification can be carried out in the presence of a base; this is especially indicated if an acid halide is used. Suitable bases are for example organic bases, such as tertiary amines, e.g. trimethylamine, triethylamine, tripropylamine, ethyldiisopropylamine and the like, or basic N-heterocycles, such as morpholine, pyridine, lutidine, DMAP, DABCO, DBU or DBN.

[0391] The acid (derivative is typically reacted with at least one equivalent of the alcohol.

[0392] The reaction can be carried out in a solvent or neat.

[0393] After completion of the reaction, the esterification product can be isolated by usual means, if necessary after neutralization (especially if an acid halide or an anhydride was used as starting material or if the acid was used in excess) and / or removal of the catalyst (especially if this is solid, e.g. one of the above-mentioned metal based catalysts or ionic exchange resins), for example by distillative, extractive or chromatographic methods. If desired, the isolated product can subsequently be further purified.

[0394] Amidation of shikimic acid, 3-dehydroshikimic acid or gallic acid to obtain compounds (II) and (III) wherein Y is NR7R8can be carried out by known means, such as reacting the respective acid (i.e. shikimic acid, 3-dehydroshikimic acid or gallic acid) or an ester of the respective acid, with an amine NHR7R8under typical amidation conditions, if desired under removal of the reaction water formed. The amidation can be carried out in the presence of a coupling reagent (generally used in an amount of 1-2 mol per mol of acid / ester), for example T3P (propanephosphonic acid anhydride) or HATLI (O-(7- azabenzotriazole-1-yl)-N,N,N’,N’-tetramethyluronium-hexafluorphosphate), and optionally also an organic base (generally used in an amount of 1-3 eq.). The amines NHR7R8are generally used in an amount of 1-3 mol per mol of acid / ester. The reaction is typically carried out in an organic solvent. Preferably an aprotic, rather polar organic solvent is used, such as tetra hydrofuran (THF), N,N-dimethylformamide (DMF) or acetonitrile (ACN). The reaction is carried out at temperatures between 0°C and reflux.

[0395] After completion of the reaction, the amidation product can be isolated by usual means, for example by distillative, extractive or chromatographic methods. If desired, the isolated product can subsequently be further purified.

[0396] To obtain compounds (II), the shikimic, 3-dehydroshikimic or gallic acid esters or amides are subjected to a hydrogenation reaction. The hydrogenation reaction is carried thusly that the carbonyl group of the ester or amide group as well as the oxo group in the 3-dehydroshikimic acid ester or amide are not reduced.

[0397] Hydrogenation of the gallic acid or amide is carried out under usual conditions for the hydrogenation of aromatic compounds.

[0398] Preferably, hydrogenation is carried out in the presence of a hydrogenation catalyst.

[0399] The hydrogenation catalyst preferably comprises a transition metal of group 7 to 11 of the Periodic Table of Elements. The group numbering relates to the IIIPAC nomenclature of 1985. Groups 7 to 11 are thus the Mn, Fe, Co, Ni and Cu groups.

[0400] More preferably the hydrogenation catalyst comprises Re, Ru, Co, Rh, Ni, Pd, Pt or Cu or a mixture of two or more of these metals. Even more preferably the hydrogenation catalyst comprises Ru, Co, Ni, Pd or Pt or a mixture of two or more of these metals. In particular, the hydrogenation catalyst comprises Ru or Pd, specifically Ru. The hydrogenation catalyst may be used either in heterogeneous phase or as homogeneous catalysts. In homogeneous catalysts, the catalyst is in the same phase as the reactants or products, whereas in heterogeneous catalysis, the phase of the catalyst differs from that of the reactants or products. A heterogeneous catalyst in terms of the present invention is thus a catalyst which is not soluble in the reaction medium.

[0401] The hydrogenation catalyst is a preferably a heterogeneous catalyst.

[0402] Heterogeneous catalysts are generally either full catalysts or supported catalysts. A full catalyst is a catalyst in which the active metal in its elementary or oxidised form makes up the major part, i.e. more than 50% by weight, in particular at least 80% by weight of the catalyst in its active form. A supported catalyst is a catalyst where the active metal is supported on a support material.

[0403] An example of a full Ru catalyst is ruthenium hydroxide, ruthenium oxide (in particular ruthenium dioxide) or a ruthenium oxide hydrate, especially a ruthenium(lll) oxide hydrate as described in DE 2132547 C2 (obtainable by reacting a Ru(lll) salt, e.g. the trichloride trihydrate, with an alkali metal hydroxide and adding during or after precipitation of the ruthenium oxide hydrate diluted hydrogen peroxide).

[0404] Preferably, the heterogeneous catalyst is a supported catalyst.

[0405] Suitable support materials are known in the art and are for example carbon, such as activated carbon, alumina, silica, silicon carbide, alumosilicates, such as zeolites; magnesium aluminium silicates, such as cordierite; magnesium silicates, such as steatite; titanium dioxide, zirconium dioxide, or organic polymers. Preference is given to carbon, alumina, silica, zeolite, cordierite, steatite, TiC>2 and ZrCh; more preference to alumina, TiC>2 and ZrC>2. In a specific embodiment, the support material is ZrC>2.

[0406] The catalyst may be applied to the support material by customary processes, for example by impregnating, wetting or spraying the support with a solution which comprises the catalyst or a suitable precursor thereof. Many supported catalysts are commercially available.

[0407] The metallic catalysts may also be used in oxidized form (e.g. in form of a metal salt or a metal oxide), which is then reduced under the hydrogenation conditions to the corresponding metals.

[0408] The catalyst loading of the active metal (e.g. of the group 7-11 transition metal), i.e. the amount of active metal in the supported catalyst, is preferably in the range of from 1 to 20% by weight, more preferably from 1 to 15% by weight, even more preferably from 1 to 10% by weight, in particular from 2 to 10% by weight, relative to the total (dry) weight of the supported catalyst. The percentages refer to the active metal only, and not to any salt or oxide or other form in which the metal is actually present. The loading can be determined analytically, for example by atomic absorption spectrometry, or can be calculated from the preparation method.

[0409] The amount of catalyst to be used depends on factors including the particular catalytically active metal and its use form, and may be determined in the individual case by those skilled in the art. Preferably, the hydrogenation catalyst is used in an amount of from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight and in particular from 0.3 to 1% by weight, based on the weight of compound (II). The percentages refer to the amount of active metal only, i.e. to the catalytically active component of the catalyst, and not to any salt or oxide or supported form in which the metal is actually present.

[0410] The reaction pressure of the hydrogenation reaction is preferably in the range from 2 to 300 bar (0.2 to 30 MPa), more preferably from 10 to 250 bar (1 to 25 MPa), even more preferably from 100 to 200 bar (10 to 20 MPa), and in particular from 150 to 200 bar (15 to 20 MPa).

[0411] The hydrogenation is effected at a temperature of preferably from 20 to 200°C, preferably from 40 to 180°C, more preferably from 100 to 150°C.

[0412] The hydrogenation is preferably effected in a suitable solvent. Suitable solvents are those which are inert under the reaction conditions, i.e. neither react with the reactant or product nor are changed themselves. In particular, suitable solvents are not themselves hydrogenated under the hydrogenation conditions. Suitable solvents include alkanes, in particular Cs-Cw-alkanes such as pentane, hexane, heptane, octane, nonane, decane and isomers thereof, cycloalkanes, in particular Cs-Cs-cycloalkanes such as cyclopentane, cyclohexane, cycloheptane or cyclooctane, open-chain and cyclic ethers such as diethyl ether, dipropyl ether, diisopropyl ether, methyl-tert-butyl ether, tetrahydrofuran or 1 ,4-dioxane, and alcohols, in particular Ci-Cs-alkanols such as methanol, ethanol, n-propanol or isopropanol. Also suitable are mixtures of the aforementioned solvents. Preferred solvents are the Ci-Cs-alkanols methanol, ethanol, n-propanol, isopropanol and mixtures thereof.

[0413] The hydrogen required for the hydrogenation may be used either in pure form or in the form of hydrogen-containing gas mixtures. However, the latter must not comprise any damaging amounts of catalyst poisons such as CO. Examples of suitable hydrogen- containing gas mixtures are those from the reforming process. However, preference is given to using hydrogen in pure form.

[0414] The hydrogenation may be configured either continuously, semi-continuously or batch- wise.

[0415] The hydrogenation is generally carried out in such a way that the starting compound is initially charged in the solvent. This reaction solution is subsequently preferably initially admixed with the hydrogenation catalyst before the introduction of hydrogen then begins. Depending on the hydrogenation catalyst used, the hydrogenation is effected at elevated temperature and / or at elevated pressure. For the reaction under pressure, the customary pressure vessels known from the prior art, such as autoclaves, stirred autoclaves and pressure reactors, may be used. When elevated hydrogen pressure is not employed, useful apparatus is the customary prior art reaction apparatus which is suitable for standard pressure. Examples thereof are customary stirred tanks which are preferably equipped with evaporated cooling, suitable mixers, introduction devices, if appropriate heat exchanger elements and inertization devices. In the case of continuous reaction, the hydrogenation may be carried out under standard pressure in reaction vessels, stirred reactors, fixed bed reactors and the like which are customary for this purpose.

[0416] On completion of hydrogenation, the catalyst and the solvent are generally removed. The heterogeneous catalyst is preferably removed by filtration or by sedimentation and removal of the upper, product-containing phase. Other removal processes for removing solids from solutions, for example centrifugation, are also suitable for removing the heterogeneous catalyst. Homogeneous catalysts are removed by customary processes for separating single-phase mixtures, for example by chromatographic methods. If appropriate, it may be necessary, depending on the catalyst type, to deactivate it before the removal. This can be effected by customary processes, for example by washing the reaction solution with protic solvents, for example with water or with Ci-Cs-alkanols such as methanol, ethanol, propanol or isopropanol, which may be basified or acidified if required.

[0417] The solvent is removed by customary processes, for example by distillation, in particular under reduced pressure.

[0418] Suitable hydrogenation conditions for the conversion of the shikimic and 3-dehydroshi- kimic acid esters or amides are similar to those described above for gallic esters / am- ides. Suitable heterogeneous catalyst systems are in this case in particular Pd on a suitable carrier, such as carbon. Enzymatic reduction using for example NADH, as described by D.J. Bougioukou in Adv. Synth. Catal. 2009, 351 , 3287-3305, is another option.

[0419] Hydrogenation of the shikimic acid, 3-dehydroshikimic acid or gallic acid esters or amides yields the compound (III). Before being used in the following steps, this can be subjected to a purification. Purification can be carried out by usual means, e.g. by extractive or chromatographic methods. Generally, however, the hydrogenation affords said compound (III) in sufficient purity for the further reaction.

[0420] If the above reactions start from shikimic acid or 3-dehydroshikimic acid, the stereochemical configuration of these compounds may be maintained in the downstream products (I. a) and (l.b). For the use of compounds (I. a) and (l.b) as surfactants, this is however of lesser importance; therefore it is not necessary to apply conditions which strictly avoid racemization.

[0421] Compounds (I. a) and (l.b) are suitable as surfactants. They are at least partially available from renewable sources and readily biodegradable, having a reduced carbon footprint.

[0422] The invention is now illustrated by the following examples.

[0423] EXAMPLES

[0424] A. Synthesis

[0425] Analyses were performed and structures were confirmed by nuclear magnetic resonance (NMR) spectroscopy.

[0426] Example 1: Synthesis of shikimic acid lauryl ester (compound (l.b), wherein R1bis OH, R2band R3bare hydrogen, and Y is -OR6with R6= lauryl)

[0427] In a 500 mL glass vessel equipped with a stirrer, reflux condenser and water separator, shikimic acid (15 g, 86.1 mmol, 1 eq) and 1-dodecanol (112 g, 603 mmol, 7 eq) were dissolved in toluene (50 g) at 50-60°C. Afterwards, para-toluene sulfonic acid (0.25 g, 1.29 mmol, 0.015 eq) was added and the temperature was increased to 140°C. The mixture was stirred under reflux for 28 h and liberated water was removed.

[0428] A sample was taken and analyzed via1H NMR spectroscopy. It showed full conversion of the shikimic acid. The reaction mixture was cooled to 80°C. By use of a rotary evaporator, the toluene was removed at 80°C and 10 mbar. The residue was dissolved in the same amount of ethyl acetate and elevated temperature. At room temperature, crystals were obtained and isolated by filtration. The crystals were again recrystallized from the 4-fold amount of ethyl acetate. The crystals were isolated by filtration and residual amounts of ethyl acetate were removed at 10 mbar.

[0429] Analysis via1H NMR showed that pure shikimic acid lauryl ester was obtained (13.7 g, 40 mmol, 46 % yield).

[0430] Example 2: Synthesis of sulfonated shikimic acid lauryl ester sodium salt (= the compound (I. a) wherein R4is hydrogen, R5is -S(O)3'Na+, R1ais OH, R2aand R3aare hydrogen, and Y is -OR6with R6= lauryl)

[0431] In a 500 mL glass vessel equipped with a stirrer and a reflux condenser, shikimic acid lauryl ester (13.6 g, 38 mmol, 1.0 eq) was dissolved in mixture of 1 ,4-dioxane (80 mL) and water (50 mL) at 60°C. The pH was adjusted to ca. 5. Afterwards, a solution of 40 wt-% sodium hydrogen sulfite in water (19.7 g, 75.9 mmol NaHSOs, 2.0 eq) was added and the mixture was heated to reflux (ca. 89°C) and stirred for 6 hours at 89°C.

[0432] A sample was taken and analyzed via1H NMR spectroscopy. After full conversion of the shikimic acid lauryl ester, the mixture was cooled to room temperature. Hydrogen peroxide (0.75 eq) was added to convert remaining sulfite into the corresponding sulfate. After full conversion of the peroxide, solids at the bottom of the vessel were filtered off. The solution was isolated. By use of a rotary evaporator, water and 1 ,4-dioxane were removed at 60°C and 10 mbar. Afterwards, residual amounts of 1 ,4-dioxane were removed by the addition of a few mL of water and removal of all liquids at 60°C and 10 mbar at a rotary evaporator.

[0433] Analysis via1H NMR showed that pure sulfonated shikimic acid lauryl ester sodium salt was obtained (16.6 g, 38 mmol, 100% yield).

[0434] 1H-NMR (CD3OD; 500 MHz): 8 = 0.88 ppm (3 H, s), 1.25 - 1.50 ppm (18 H, m), 1.6 - 1.7 ppm (2H, m), 1.75 - 2.38 (2 H, m), 3.05 - 3.17 (1 H, m), 3.40 - 4.30 ppm (5 H, m), 4.45 - 4.60 ppm (1 H, m)

[0435] The product was dissolved in water to obtain an aqueous surfactant solution with 20 wt- % active content. The pH was adjusted to a value of 6-7.

[0436] B. Surfactant properties

[0437] To determine surfactant properties of the compounds according to the invention, measurements of critical micelle concentration (CMC), surface tension, foam volume and interfacial tension were carried out as follows and the results are compiled in the table below. Critical micelle concentration (CMC)

[0438] The critical micelle concentration (CMC) was determined according to EN 14370 (Wil- helmy Plate). According to this method, a series of aqueous solutions of the compound to be tested with increasing concentrations, ranging from well below to well above the expected value, were prepared automatedly in deionized water at pH 9. Each solution was poured into a clean, temperature-controlled vessel (at 23°C). The Wilhelmy plate was slowly lowered until it just touched the liquid surface, and the force due to surface tension was recorded. Surface tension was calculated from the measured force. By plotting the surface tension as a function of the concentration, the CMC was calculated by applying two tangents to the curves above and below the CMC and determining the point of intersection of the two tangents.

[0439] Surface tension

[0440] The surface tension was measured at 23°C, at 1 g / L in deionized water at pH 9 in accordance with DIN EN 14370:2004 (Wilhelmy Plate), as described above.

[0441] Foam volume

[0442] The foam volume was measured according to EN 12728 at 2 g / L and 40°C at pH 9 in deionized water (DI water).

[0443] Interfacial tension

[0444] The interfacial tension vs. hexadecane and olive oil, respectively, was measured at 23°C after 10 min, at 1 g / L in deionized water with a DataPhysics instrument OCA25 (pendant drop method).

[0445] Table: Properties of the inventive compounds:

Claims

Claims1. The use of a compound of the formula (I. a) or (l.b)whereR1ais a group -OR1aaor an oxo group (=0);R1bis a group -OR1bbor an oxo group (=0);R1aa, R2a, R3a, R1bb, R2band R3b, independently of each other, are hydrogen or a group -S(O)3H or -S(O)3'M+, where M+is a metal cation equivalent or an ammonium cation;R4and R5are hydrogen or one of R4and R5is a group -S(O)3H or -S(O)3'M+, where M+is a metal cation equivalent or an ammonium cation; and the other is hydrogen; andY is a group -OR6or NR7R8, whereR6is Ce-Cso-alkyl or Ce-Cso-alkenyl;R7is Ce-Cso-alkyl or Ce-Cso-alkenyl; andR8is hydrogen, Ci-Cso-alkyl or Cs-Cso-alkenyl; or of a mixture of different compounds (I. a) and / or (l.b), or of a stereoisomer of the compound (I. a) or (l.b), or of a mixture of different stereoisomers of the compounds (I. a) and / or (l.b) as a surfactant.

2. The use according to claim 1 , where in compounds (I. a)R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, orR1ais oxo and at least one of R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3'M+; where preferably R1ais oxo, one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen, and R2aand R3aare independently hydrogen or a group -S(O)3H or -S(O)3'M+; orR1ais OR1aaand at least one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, with the proviso that at most one of R4and R5is a group -S(O)3H or -S(O)3'M; where preferably R1ais OR1aa, one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other is hydrogen, and R1aa, R2aand R3aare independently hydrogen or a group -S(O)3H or -S(O)3'M+.

3. The use according to claim 2, where in compounds (I. a)R1ais oxo or OH, R2a, R3a, R4and R5are hydrogen, orR1ais oxo and on average one of R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+; and the other three of R2a, R3a, R4and R5are hydrogen, where preferably R1ais oxo, one of R4and R5is a group -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+, and the other is hydrogen, and R2aand R3aare hydrogen; orR1ais OR1aaand on average one of R1aa, R2a, R3a, R4and R5is a group -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+; and the other four of R1aa,R2a, R3a, R4and R5are hydrogen; where preferably R1ais OR1aa, one of R4and R5is a group -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+, and the other is hydrogen, and R1aa, R2aand R3aare hydrogen.

4. The use according to any of the preceding claims, where in compounds (I. a) one of R4and R5is -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+; and the other of R4and R5is hydrogen.

5. The use according to any of claims 3 or 4, where in compounds (I. a) one of R4and R5is -S(O)3'M+and the other of R4and R5is hydrogen; R2aand R3aare hydrogen; and R1ais oxo or OR1aa, wherein R1aais hydrogen; where preferably R1ais OR1aa, wherein R1aais hydrogen.

6. The use according to any of the preceding claims, where in compounds (l.b) R1bis oxo and R2band R3bare hydrogen; orR1bis OH and R2band R3bare hydrogen; where preferably R1bis OH and R2band R3bare hydrogen.

7. The use according to any of the preceding claims, where the compound of the formula (I. a) is a compound of the formula (l.a.1), (I. a.2) or (I. a.3), and the compound of the formula (l.b) is a compound of the formula (l.b.1), (l.b.2) or (l.b.3)8. The use according to any of the preceding claims, where M+is an alkali metal cation or an alkaline earth metal cation equivalent, preferably Na+, K+, (Mg2+)i / 2 or (Ca2+)i / 2, more preferably Na+or K+, even more preferably Na+.

9. The use according to any of the preceding claims, where R6and R7, independently of each other, are Cs-Cso-alkyl, preferably C -Cis-alkyl, more preferably linear C -Cis-alkyl, in particular linear Cw-C -alkyl; and R8is hydrogen; where more particularly R6and R7, independently of each other, are n-decyl, n- dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl; and R8is hydrogen.

10. The use according to any of the preceding claims, where Y is OR6.11 . The use according to any of the preceding claims, of a compound (I. a), wherein one of R4and R5is -S(O)3H or -S(O)3'M+, preferably -S(O)3'M+; and the other of R4and R5is hydrogen; R2aand R3aare hydrogen; R1ais oxo or OR1aa, wherein R1aais hydrogen; Y is OR6and R6is Cw-C -alkyl; where preferably one of R4and R5is -S(O)3'M+, where M+is an alkali metal cation; and the other of R4and R5is hydrogen; R2aand R3aare hydrogen; R1ais OR1aa, wherein R1aais hydrogen; Y is OR6and R6is C -C -alkyl.

12. The use according to any of the preceding claims, of a compound (l.b), wherein R1bis OH, R2band R3bare hydrogen, Y is OR6and R6is C -C -alkyl.

13. The use according to any of the preceding claims, where at least a part of the compounds (I. a) and (l.b) is derived from gallic acid, shikimic acid or 3-dehydro- shikimic acid which is obtained from a renewable source and / or is derived from an alkanol R6OH or an amine NHR7R8which is obtained from a renewable source, where preferably in the compounds (I. a) and (l.b) at least 20 mol-% of the carbon atoms, relative to the total amount of carbon atoms in the compounds (I. a) and (l.b), stem from a renewable source.

14. The use according to any of the preceding claims, in homecare compositions, l&l cleaning compositions, personal care compositions or pesticide adjuvant compositions; or for stabilizing oil-in-water emulsions or aqueous dispersions.

15. A surfactant composition comprising a compound of the formula (I. a) or (l.b) as defined in any of claims 1 to 13 or a mixture of different compounds (I. a) and / or (l.b), or a stereoisomer of the compound (I. a) or (l.b), or a mixture of different stereoisomers of the compounds (I. a) and / or (l.b), and at least one component selected from the group consisting of: water, organic solvents, surfactants different from the compounds (I. a) and (l.b), fragrances, antimicrobial agents, seques- trants, enzymes, enzyme stabilizers, hydrotropic agents, bleaching agents, dyes, pigments, pH adjusting agents, pearlescents, opacifiers, viscosity modifiers, and inorganic salts.

16. The surfactant composition according to claim 15, where the compound of the formula (l.b) is none of the compounds selected from the group consisting of Ce- Ci2-alkylesters of shikimic acid, C6-Ci2-alkylesters of 3-dehydroshikimic acid, N- hexadecyl shikimic acid amide and N-tridecyl shikimic acid amide.

17. The surfactant composition according to any of claims 15 or 16, where in compounds of the formula (l.b) at least one of R1bb, R2band R3bis a group -S(O)3H or -S(O)3-M+.

18. The surfactant composition according to any of claims 15 to 17, which is selected from the group consisting of homecare compositions, l&l cleaning compositions, personal care compositions and pesticide adjuvant compositions.

19. A compound of the formula (I. a) or of the formula (l.b) or a stereoisomer of the compound (I. a) or (l.b) as defined in any of claims 1 to 13; except for following compounds:- compounds (l.b) wherein R1ais OH or oxo, R2aand R3aare hydrogen, Y is OR6and R6is dodecyl;- compound (l.b) wherein R1ais oxo, R2aand R3aare hydrogen, Y is OR6and R6is n-hexyl;- compound (l.b) wherein R1ais OH, R2aand R3aare hydrogen, Y is NR7R8, R7is n-hexadecyl and R8is hydrogen.

20. The compound according to claim 19, where the compound of the formula (l.b) is none of the compounds selected from the group consisting of C6-Ci2-alkylesters of shikimic acid, C6-Ci2-alkylesters of 3-dehydroshikimic acid, N-hexadecyl shi- kimic acid amide and N-tridecyl shikimic acid amide.

21. The compound according to any of claims 19 or 20, where in compounds of the formula (l.b) at least one of R1bb, R2band R3bis a group -S(O)3H or -S(O)3'M+.

22. A method for preparing a compound of the formula (I. a) as defined in any of claims 1 to 5, 7 to 11 , 13 and 19, wherein one of R4and R5is a group -S(O)3H or -S(O)3'M+and the other of R4and R5is hydrogen, comprising(i.1) reacting a compound (II)where Y is as defined in any of claims 1 , 9 to 11 and 19 and R1ais oxo or OR1aa, where R1aais hydrogen, with a sulfonation agent; and(ii.1) if desired reacting the compound (I. a) obtained in step (i.1) with a base to obtain a compound (I. a) wherein one of R4and R5is a group -S(O)3'M+and the other of R4and R5is hydrogen, and where optionally also one of R1aa(if present) R2aand R3ais a group -S(O)3'M+.

23. A method for preparing a compound of the formula (I. a) as defined in any of claims 1 to 5, 7 to 11 , 13 and 19, wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3aa group -S(O)3H or -S(O)3'M+, comprising (i.2) reacting a compound (III)where Y is as defined in any of claims 1 , 9 to 11 and 19 and R1ais oxo or OR1aa, where R1aais hydrogen, with a sulfonation agent to obtain a compound (I. a) wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3ais a group -S(O)3H; and(ii.2) if desired reacting the compound (I. a) obtained in step (i.2) with a base to obtain a compound (I. a) wherein R4and R5are hydrogen and at least one of R1aa(if present), R2aand R3ais a group -S(O)3'M+.

24. The method according to any of claims 22 or 23, where the sulfonation agent is selected from the group consisting of hydrogensulfites, chlorosulfonic acid, sulfur trioxide (SO3), mixtures of sulfur trioxide (SO3) with air; sulfamic acid, and oleum (fuming sulfuric acid; sulfuric acid with excess sulfur trioxide), where in case of the method according to claim 22 the sulfonation agent is preferably selected from the group consisting of hydrogensulfites, more preferably alkali metal hydrogensulfites, in particular sodium hydrogensulfite; and in case of the method according to claim 23 the sulfonation agent is preferably selected from the group consisting of chlorosulfonic acid, sulfur trioxide (SO3), mixtures of sulfur trioxide (SO3) with air; sulfamic acid, and oleum (fuming sulfuric acid; sulfuric acid with excess sulfur trioxide); and / or where the base is selected from alkali or alkaline earth metal hydroxides, alkali or alkaline earth metal carbonates, alkali or alkaline earth metal hydrogencarbonates, alkali or alkaline earth metal phosphates or ammonia, preferably from alkali metal hydroxides, more preferably from NaOH and KOH, and in particular from NaOH.

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