New sulfonate compounds

Abstract

The present invention relates to a compound represented by formula (I) or (II): JPEG2024535892000054.jpg128145 [In the formula, Each R 1 is selected from hydrocarbon radicals having 4 to 26 C atoms and optionally at least one O or S atom; R 2 Or R 5 are each independently selected from hydrogen and a hydrocarbon radical having 1 to 26 C atoms and optionally at least one O or S atom; Each R 6 are independently selected from hydrogen and a hydrocarbon radical having 1 to 6 carbon atoms, where optionally two radicals R 6 may be connected, as shown by the dashed line, to form a 5- or 6-membered ring that includes the carbonyl carbon atom; and Each X is independently H + Monovalent or polyvalent cations, including X n+ where n is ≧1, and where in formula (I), optionally both X's together may represent a multivalent cation. and novel sulfonate compounds according to Processes for their production and their use as surfactants, Regarding.

Description

[Technical field]

[0001] The present invention relates to novel sulfonate compounds, processes for their preparation, and their use as surfactants. [Background technology]

[0002] 2. Background of the Invention Lignin is an abundant aromatic biopolymer, the structure of which is mainly based on three substituted phenols, the so-called monolignols (p-coumaryl, coniferyl and sinapyl alcohol), characterized by a variety of different C-O and C-C bonds that form an amorphous three-dimensional structure. Various methods have been developed that allow the catalytic decomposition of lignin by depolymerization to obtain industrially usable monomolecular phenol and / or benzaldehyde derivatives. In addition to monomers, the products of these depolymerization processes may also include di-, tri- and oligomers of phenols.

[0003] More recently, various methods have been developed that allow for the selective depolymerization of lignin, mainly involving reductive or oxidative reaction strategies. The former usually produce phenols, guaiacol or syringol derivatives with aliphatic radicals, usually 1 to 3 carbon atoms in length, bearing alcohol, aldehyde, ester and / or ketone functionality, whereas the latter usually give aromatic aldehydes, such as vanillin and syringaldehyde, or similarly functionalized guaiacol and syringol derivatives. The main products of such depolymerization processes include guaiacol and syringol, or vanillin and syringaldehyde, respectively, which often bear one or more alkyl and / or alkoxy substituents on the aromatic ring.

[0004] All the mentioned lignin degradation products are valuable biologically based resources from which many different products have been produced in recent years. Our research shows that surfactants are few and far between, but even in this field there is a need for products that can be synthesized based on non-edible, renewable raw materials.

[0005] Against this background, the object of the present invention is the synthesis of new chemical compounds particularly suitable for use as surfactants, by functionalizing these products of lignin degradation and similar compounds, preferably in an environmentally friendly manner. Summary of the Invention

[0006] In a first aspect, the present invention provides a compound represented by formula (I) or (II):

[0007] [ka]

[0008] [In the formula, Each R 1 is selected from linear, branched or cyclic hydrocarbon radicals having from 4 to 26 carbon atoms, where optionally at least one carbon atom is replaced by an oxygen or sulfur atom; R 2 Or R 5 are each independently selected from hydrogen and a linear, branched or cyclic hydrocarbon radical having from 1 to 26 carbon atoms, optionally wherein at least one carbon atom is replaced by an oxygen or sulfur atom; Each R 6 are independently selected from hydrogen and saturated hydrocarbon radicals having 1 to 6 carbon atoms, where optionally two radicals R 6 may be connected, as shown by the dashed line, to form a 5- or 6-membered ring that includes the carbonyl carbon atom; and Each X is independently H + Monovalent or polyvalent cations, including X n+where n is ≧1, and where in formula (I), optionally both X's together may represent a multivalent cation. This object is achieved by providing novel sulfonate compounds according to the invention.

[0009] The inventors have found that such disulfonate compounds according to formula (I) or the corresponding monosulfonates according to formula (II) can be prepared in a relatively simple and environmentally friendly manner from readily available lignin degradation products and are highly suitable as surfactants. Due to the high hydrophilicity of the sulfonate group and the hydrophobicity of the aromatic radical R 1 Or R 5 Even a single digit number of carbon atoms in is sufficient to confer the required amphiphilicity to the compound.

[0010] However, the radical R 1 Or R 5 The number of carbon atoms in is preferably at least 9. This means that in the compound according to formula (I), there are two sulfonate groups -SO 3 It is particularly favorable in terms of hydrophobicity if X is attached to the central pentanone. However, the fact that the main products of lignin depolymerization include derivatives of vanillin and syringaldehyde, which, as mentioned at the beginning, often have one or two additional lower alkyl and / or lower alkoxy substituents, suggests that R 2 Or R 4 already contains some carbon atoms, so the radical R 1 Or R 5 This simplifies the synthesis of the sulfonate compounds of the invention having at least 9 carbon atoms in the formula (I), so that the preparation process according to the invention only requires the etherification of the free phenolic OH groups of such vanillin and syringaldehyde derivatives with readily available and biodegradable fatty alkyl radicals.

[0011] On the one hand, fatty alcohols naturally exist in both saturated and unsaturated form, i.e. with one or more C=C double bonds, and on the other hand, as mentioned at the beginning, lignin degradation products can have more than one aromatic ring as well as non-aromatic rings (e.g. dioxolanes) as substituents, so that R 1 Or R 5 The definition includes both saturated and unsaturated as well as cyclic radicals.

[0012] The fact that in addition to the disulfonate compounds according to formula (I), also monosulfonates according to formula (II) are included in the present invention is due to the sulfonation by addition of bisulfite in step 3) of the process of the present invention, which is explained in more detail in connection with the second aspect of the present invention and is demonstrated by the examples below.

[0013] It should be noted that in general, in this specification, "sulfonate" is understood not only as a salt of a sulfonic acid group, but also as the respective free acid, unless the context requires otherwise. This is because the definition of the counterion X above explicitly includes H + This is evident from the fact that, when the novel compounds are used as surfactants according to the third aspect of the invention, the respective free acids also ionize in an aqueous environment, thereby forming sulfonic acid groups in situ.

[0014] Radical R 1 Or R 5The lower and upper limits for the number of carbon atoms in refer to the preference for the use of fatty alkyl radicals for the etherification of the free phenolic OH groups in the starting products, the chain lengths of which are specified in the literature as lower limits of 4 to 6 and upper limits of 22 to 26. According to the invention, for the fatty alkyl radicals introduced in the synthesis by etherification, a maximum length of 18 carbon atoms is preferred, and for the alkyl or alkoxy radicals or optionally alkylthio radicals already bonded to the aromatics in the starting materials, a maximum length of 4 carbon atoms is preferred, with the radical R in the ortho position to the phenolic OH group being preferred. 2 and R 3 This is especially true for

[0015] The option that some carbon atoms may be replaced by oxygen or sulfur also refers primarily to the substitution pattern of the starting compound, preferably obtained by lignin depolymerization, which, as mentioned at the beginning, may contain various oxygen-containing functionalities, sometimes also their sulfur analogues. Other heteroatoms, such as halogens and nitrogen, are rarely present in such compounds. Therefore, for the purposes of the present invention, heteroatoms other than oxygen and sulfur do not have to be taken into account.

[0016] Thus, in some preferred embodiments of the present invention, R 1 is C 6 -C 22 Alkyl, more preferably C 8 -C 18 Alternatively or additionally, in some preferred embodiments, R 2 and R 3 is hydrogen, C 1 -C 22 Alkyl, and C 1 -C 22 From alkoxy, more preferably hydrogen, C 1 -C 4 Alkyl, and C 1 -C 4 alkoxy; for example, R 2 and R 3Alternatively or additionally, in some preferred embodiments, one of R is hydrogen and the other is methoxy, or both radicals are methoxy. 4 and R 5 is selected from hydrogen, methyl, and methoxy. Alternatively or additionally, in some preferred embodiments, the radical R 6 is selected from hydrogen, methyl, and ethyl, or may be joined together to form a 5- or 6-membered ring containing the carbonyl carbon. Alternatively or additionally, in some preferred embodiments, each X is selected from H + , Na + , K + , N.H. 4 + or an organic ammonium ion.

[0017] In a particularly preferred embodiment, with respect to the synthesis method, R 1 Or R 5 Both radicals in R represent the same radical, i.e., both radicals R 1 is the same C 8 -C 18 Represents an alkyl radical, both radicals R 2 and both radicals R 3 is hydrogen or the same C 1 -C 4 Alkyl or the same C 1 -C 4 represents an alkoxy radical, and both radicals R 4 and both radicals R 5 represents either hydrogen, methyl or methoxy. Furthermore, in the disulfonate compounds according to formula (I), both radicals X also represent the same counterion, i.e., both are the same monovalent cation X + or both X's together represent the same multivalent cation X n+ In such cases, it is most preferable to use Ca 2+ or Mg 2+ A divalent cation such as X 2+In these embodiments, the novel disulfonate compounds according to formula (I) have mirror symmetry about an axis passing through the central keto group (i.e., the vertical axis in the formula drawing).

[0018] Thus, in some particularly preferred embodiments the following applies: Both radicals R 1 But the same C 8 -C 18 represents an alkyl radical; Both radicals R 2 and both radicals R 3 are each hydrogen or methoxy; Both radicals R 4 and both radicals R 5 are each hydrogen; Both radicals R 6 are each hydrogen or methyl, or are joined together to form an ethylene or propylene radical, i.e., a 5- or 6-membered ring containing the carbonyl carbon; and The radical X is, respectively, H + , Na + , NH4 + or an organic ammonium ion, most preferably (2-hydroxyethyl)trimethylammonium (choline) or triethanolammonium.

[0019] Most preferably, the sulfonate compound according to the first aspect of the invention is selected from the following compounds:

[0020] 1,5-Bis(3-methoxy-4-octyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (1)

[0021] [ka]

[0022] 1,5-Bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (2)

[0023] [ka]

[0024] 1,5-Bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (3)

[0025] [ka]

[0026] 1,5-Bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (4)

[0027] [ka]

[0028] 1,5-Bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (5)

[0029] [ka]

[0030] 1,5-Bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (6)

[0031] [ka]

[0032] 1,5-Bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (7)

[0033] [ka]

[0034] 1,5-Bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (8)

[0035] [ka]

[0036] 1,5-Bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (9)

[0037] [ka]

[0038] 1,5-Bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid dipotassium salt (10)

[0039] [ka]

[0040] 1,5-Bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid dicholine salt (11)

[0041] [ka]

[0042] 1,5-Bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid bis(triethanolammonium) salt (12)

[0043] [ka]

[0044] 1,1'-(2-oxocyclopentane-1,3-diyl)-bis[(3-methoxy-4-octyloxyphenyl)methanesulfonic acid ammonium salt] (13)

[0045] [ka]

[0046] In a second aspect, the present invention relates to a method for producing a sulfonate compound according to the first aspect, comprising the steps of: 1) In an organic solvent, in the presence of a base, a Williamson etherification reaction is carried out to obtain a compound represented by the following formula (III):

[0047] [ka]

[0048] [In the formula, R 2 Or R 5 are each independently selected from hydrogen and a linear, branched or cyclic hydrocarbon radical having from 1 to 26 carbon atoms, optionally in which at least one carbon atom is replaced by an oxygen or sulfur atom. The 4-hydroxybenzaldehyde derivative according to the formula R 1 -Y(wherein, R 1is selected from linear, branched or cyclic hydrocarbon radicals having 4 to 26 carbon atoms, where optionally at least one carbon atom may be replaced by an oxygen or sulfur atom, and Y represents a leaving group selected from a halide and a sulfonate, to give a compound of formula (IV):

[0049] [ka]

[0050] to obtain the corresponding ether;

[0051] 2) The ether of formula (IV) is reacted with half an equivalent of acetone or a carboxylic acid of formula (V) by a Claisen-Schmitt double crossed aldol condensation reaction in an organic solvent using an acidic or basic catalyst.

[0052] [ka]

[0053] [In the formula, each R 6 are independently selected from hydrogen and saturated hydrocarbon radicals having 1 to 6 carbon atoms, where optionally two radicals R 6 may be connected, as shown by the dashed lines, to form a 5- or 6-membered ring that includes the carbonyl carbon atom. by reacting with an acetone derivative according to formula (VI):

[0054] [ka]

[0055] to obtain the corresponding unsaturated ketone; 3) reacting the ketone of formula (VI) with a sulfonating agent in an alcoholic solvent in order to add one or two equivalents of hydrogen sulfite to the double bond of the ketone of formula (VI), optionally followed by ion exchange of the mono- or disulfonate thus obtained and the addition of a given counterion X n+ where n is ≧1 to obtain a compound of formula (I) or a sulfonate compound of formula (II); Includes.

[0056] Thus, according to the present invention, it is possible to synthesize novel sulfonate compounds from hydroxybenzaldehyde derivatives according to formula (III) by a relatively simple and inexpensive method involving a series of known individual reactions. In a preferred embodiment, the starting compounds are readily available products of lignin depolymerization, such as optionally substituted vanillin or syringaldehyde, and the method is carried out in the most environmentally friendly way possible.

[0057] In some preferred embodiments of the process of the present invention, in step 1), chloride or bromide, most preferably bromide, is used as the leaving group Y; and / or K 2 CO 3 As the base, most preferably 2 equivalents of K 2 CO 3 and / or acetonitrile is used as the organic solvent, most preferably at reflux temperature.

[0058] As leaving group Y, sulfonates such as mesylates or tosylates can be used; however, their use is uneconomical since long-chain fatty alcohol sulfonates are already surfactants, which is why chlorides or bromides, especially bromides, are preferred. After a series of tests with other polar aprotic solvents such as acetone, diethyl ether and DMF, acetonitrile proved to be a very suitable solvent, especially under reflux, since it gave the best conversion and simplified the subsequent purification of the product. For the latter reason, hydroxybenzaldehyde derivatives according to formula (III) can be reacted with hydroxybenzaldehyde derivatives according to formula R 1It is preferred to use a slight excess, for example 10-15 mol % excess, relative to the compound of -Y. 2 CO 3 Combined with the use of , this allows the KBr formed as a by-product to be collected and quasi-recycled, i.e., according to the formula R 1 This provides the added advantage that the KBr can be used to synthesize other desired compounds, which are preferably fatty alkyl bromides, and can be readily prepared from fatty alcohols using this KBr.

[0059] In some preferred embodiments of the method of the present invention, in step 2), the basic catalyst is lithium hydroxide monohydrate LiOH.H 2 O is most preferably used in an amount of 1-10 mol %; and / or as the organic solvent a lower alcohol, ether, or mixtures thereof, most preferably isopropanol, most preferably at a thoroughly tested reaction temperature of 40-50° C.

[0060] As a basic catalyst, other bases such as NaOH or KOH can also be used, or the reaction can be carried out using a phase transfer catalyst, for example, tetra-n-butylammonium bromide (TBAB) as a catalyst. However, we have found that lithium hydroxide monohydrate LiOH.H 2 The best results in terms of conversion and reaction time were achieved by using O. Similarly, instead of the preferred solvent isopropanol, other alcohols such as ethers, MeOH or EtOH, or mixtures of alcohols with water or diethyl ether can also be used. However, when using isopropanol, it is not necessary to heat the reaction mixture to its reflux temperature (82.5° C.) to achieve high conversion in a short time.

[0061] In some preferred embodiments of the method of the present invention, in step 3), Bisulfite or disulfite, preferably sodium disulfite 2 S 2 O 5, Calcium hydrogen sulfite Ca(HSO 3 ) 2 , Ammonium hydrogen sulfite NH 4 HSO 3 or trimethylammonium sulfite [(CH 3 ) 3 N] 2 SO 3 is used as the sulfonating agent; and / or a mixture of lower alcohol and water, more preferably aqueous methanol or isopropanol, is used as the alcohol solvent; and / or An amine, more preferably triethylamine, triethanolamine or choline hydroxide, is used as the catalyst.

[0062] In a particularly preferred embodiment, the bisulfite or disulfite is used in an amount of 3 bisulfite equivalents, respectively based on the ketone of formula (VI), the amine catalyst is used in an amount of at least 20 mol%, and aqueous isopropanol is used as the solvent under reflux to obtain the disulfonate compound according to formula (I). For the synthesis of the monosulfonate compound according to formula (II), the bisulfite or disulfite is used in an amount of only one bisulfite equivalent, in order to add only one sulfonic acid group to one of the two double bonds of the ketone according to formula (VI). It is also possible to prepare a mixture of the disulfonate according to formula (I) and the monosulfonate according to formula (II) by varying the amount of bisulfite equivalent, from which the two isolated products obtained or the mixture itself can be used as a surfactant, optionally after ion exchange.

[0063] Unless the desired counterion has already been introduced into the sulfonate compound according to formula (I) or (II) during the sulfonation process, for example by using a corresponding amine as a catalyst in step 3), the resulting sulfonate adduct is preferably first subjected to ion exchange using an acidic ion exchange resin and water elution, optionally with the predetermined counterion X, in order to convert the sulfonate group into a free sulfonic acid group. n+to give the respective desired sulfonate compound according to formula (I) or (II).

[0064] In a particularly preferred embodiment of the process of the present invention, steps 2) and 3) are carried out as a one-pot synthesis without isolating the ketone of formula (VI) by carrying out both reactions in the same lower alcohol as solvent, for example in an alcohol solvent, in particular isopropanol, at 45° C. for a reaction time of 12 h, 10 mol % LiOH.H as basic catalyst. 2 After completion of the double cross-aldol condensation reaction by using O, a sulfonating agent in the form of an aqueous solution, e.g., NaHSO 3 Simply add a basic catalyst, an amine such as triethylamine or the desired amine already as counterion, and optionally an additional amount of the same alcohol solvent. The mixture is then refluxed, most preferably for a reaction time of 12-14 h. The progress of the reaction can be monitored, for example, by the gradual disappearance of the color of the reaction mixture, for example the intense yellow color caused by the conjugated aromatic structure of the ketone of formula (VI).

[0065] In a preferred embodiment, the reaction mixture containing the sulfonate compound of the present invention according to formula (I) or (II) is first heated at room temperature with O 2 to oxidize excess sulfite to sulfate. 2 is introduced into the reactor, then n-pentane is added, and most of the water and lower alcohols are removed by distilling off the ternary azeotrope of water, lower alcohols, especially isopropanol, and pentane, preferably using a Dean-Stark water separator at an average temperature of, for example, 40-60°C. This is then dried in a rotary evaporator under vacuum to obtain a slightly yellowish solid residue. This is then preferably extracted with acetone, CHCl, for example using a Soxhlet extractor. 3 , C.H. 2 Cl 2 or Et 2 Purify by extraction with an organic solvent such as O until decolorized.

[0066] And in a third aspect, the present invention provides a compound comprising a radical R 1 Or R 5 The present invention relates to the use as surfactants of novel sulfonate compounds according to formula (I) or (II), wherein the total number of carbon atoms is at least 9. EXAMPLES

[0067] The present invention will now be described in more detail by means of examples, which should not be construed as limiting the scope of protection. For illustrative purposes, vanillin was used as a representative model compound of typical lignin depolymerization products, preferred as starting material in the process according to the invention, and was converted into a sulfonate compound according to the invention. Further examples using its methoxy derivative, syringaldehyde, another typical aromatic aldehyde as a decomposition product of lignin, are currently the subject of further experiments carried out by the inventors.

[0068] [ka]

[0069] According to the following reaction scheme A, vanillin (III) is first reacted with a series of different fatty alkyl halides R 1 -Y, then the ether of formula (IV) thus obtained is subjected to a double cross-aldol condensation reaction with half an equivalent of acetone or cyclopentanone (as indicated by the dashed bond) to obtain the doubly unsaturated ketone of formula (VI), and finally the addition of bisulfite to obtain the corresponding sulfonate compound according to the invention. In the last step, up to now, only two equivalents of bisulfite were added to both double bonds of the ketone to obtain the disulfonate according to formula (I). However, it is clear to the skilled person that the corresponding monosulfonate according to formula (II) or a mixture of both can also be obtained in a similar manner, using only a smaller amount of sulfonating agent, as already mentioned above.

[0070] Reaction Scheme A

[0071] [ka]

[0072] Example 1 Preparation of 1,5-bis(3-methoxy-4-octyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (1)

[0073] [ka]

[0074] Step 1: Vanillin (6.39 g, 42 mmol) was dissolved in 1-bromooctane (6.76 g, 35 mmol) and oven-dried K 2 CO 3 The mixture was refluxed in 100 mL of acetonitrile under a nitrogen atmosphere for 48 h. The solvent was then removed on a rotary evaporator, and the resulting residue was dissolved in diethyl ether (Et 2 The organic phase was redissolved in 200 mL of a 1:1 mixture of NaOH (pH 7.0) and petroleum ether (bp: 40-60° C.), mixed with 50 mL of 0.5 M NaOH, and then washed with 50 mL of water. 2 SO 4 After that, the solvent was distilled off under vacuum and the residue was thoroughly dried in a vacuum desiccator to give the alkylated vanillin, 3-methoxy-4-octyloxybenzaldehyde, as a white powder (yield: 9.13 g; 98.7% of theory).

[0075] Step 2: 4-Octyloxy-3-methoxybenzaldehyde (1.85 g, 7 mmol) was dissolved in 14 mL of isopropanol with lithium hydroxide monohydrate (LiOH.H) as catalyst. 2The mixture was reacted with acetone (0.20 g, 3.5 mmol) in the presence of 2H2O (14.7 g, 0.35 mmol) at 45 °C for 12 h. The solid precipitate was then centrifuged, washed three times with 6 mL of MeOH, and dried under vacuum to give the double adduct 1,5-bis(3-methoxy-4-octyloxyphenyl)penta-1,4-dien-3-one as a yellow powder (yield: 1.65 g; 85.4% of theory).

[0076] Step 3: Variant 3.1 1,5-Bis(3-methoxy-4-octyloxyphenyl)penta-1,4-dien-3-one (1.1 g, 2 mmol) was dissolved in 22 mL of isopropanol in the presence of triethylamine (0.04 g, 0.4 mmol) under reflux for 14 h and 6 mL of sodium hydrogen sulfite (NaHSO). 3 The mixture was reacted with a 1M aqueous solution of 1M NH 3 . The solid precipitate was then centrifuged and washed with MeOH. The combined organic phase was filtered through a 0.2 μm syringe filter, concentrated under reduced pressure, and then passed through a bed of freshly activated acid ion exchange resin (DOWEX® 50WX8-100), washed three times with 50 mL of water, and then washed with concentrated NH 3 . 4 A slight excess of OH solution was added to generate the ammonium salt, which was filtered off and thoroughly dried in a vacuum desiccator to give the title compound (1) as a white solid (yield: 1.34 g; 89.2% d.Th.).

[0077] Variant 3.2 1,5-Bis(3-methoxy-4-octyloxyphenyl)penta-1,4-dien-3-one (28 mg, 0.05 mmol) was dissolved in 0.1 mL of sodium hydrogen sulfite (NaHSO) using a Teflon-coated stir bar in a microwave tube. 3 and triethylamine (1 mg, 0.01 mmol), tightly sealed, and heated in a microwave reactor at 140° C. for 45 min. The reaction mixture was then dried under vacuum and a crude sample was dissolved in MeOD for analysis by NMR spectroscopy.

[0078] 1 H-NMR: δ H (700 MHz, MeOD) 6.97 (d, 1H, (C6,C12)), 6.89 (s, 1H, (C6 m , C12 m )), 6.78 (m, 2H (C3, C4, C8, C9)), 6.70 (m, 2H, (C3 m , C4 m , C8 m , C9 m )), 4.33 (m, 1H, (C13, C18)), 4.26 (m, 1H, , (C13 m , C18 m )), 3.96 (m, 4H, (C33, C41)), 3.81 (s, 3H, (C20, C22)), 3.76 (s, 3H, (C20 m , C22 m )), 3.34-3.25 (m, 4H, (C14, C16)), 1.78 (m, 4H, (C34, C42)), 1.48 (m, 4H, (C35, C43)), 1.35 (m, 17H (C36, C37, C38, C39, C44, C45, C46, C47)), 0.92 (t, 6H (C40, C48)). 13 C-NMR: δ C (176 MHz, MeOD) 207.4 (C15 m ), 206.8 (C15), 150.3 (C1, C11), 150.1 (C1 m , C11 m ), 149.4 (C2, C10), 149.3 (C2 m , C10 m ), 130.5 (C5, C7), 130.3 (C5 m , C7 m ), 123.0 (C4, C8), 122.5 (C4 m , C8 m ), 114.8 (C6, C12), 114.1 (C3, C9), 113.9 (C3 m , C9 m), 70.2 (C33, C41), 70.1 (C33 m , C41 m ), 62.6 (C13 m , C18 m ), 62.3 (C13, C18), 56.4 (C20, C22), 56.3 (C20 m , C22 m ), 46.6 (C14 m , C16 m ), 46.0 (C14, C16), 33.1 (C34 m , C42 m ), 33.0 (C34, C42), 30.6 (C35 m , C43 m ), 30.5 (C35, C43), 30.5 (C36, C44), 30.5 (C36 m , C44 m ), 30.5 (C37 m , C45 m ), 30.4 (C37, C45), 27.2 (C38 m , C46 m ), 27.2 (C38, C46), 23.8 (C39 m , C47 m ), 23.7 (C39, C47), 14.5 (C40, C48). Elemental analysis: Expected: C, 56.13; H, 8.07; N, 3.74; S, 8.56; Measured: C, 55.13; H, 8.33; N, 3.63; S, 8.36 HRMS: (ESI + , m / z) C 35 H 61 N 2 O 11 S 2 [M+H] + Calculated value: 749.37168; Measured value: 749.370948.

[0079] Example 2 Preparation of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (2)

[0080] [ka]

[0081] Step 1: The reaction was carried out in a manner similar to that of Example 1, except that 1-bromododecane was used instead of 1-bromooctane, to give 4-dodecyloxy-3-methoxybenzaldehyde as a cream-colored powder (yield: 10.85 g; 96.8% of theory).

[0082] Step 2: The reaction was carried out in a manner similar to that of Example 1 to give 1,5-bis(4-dodecyloxy-3-methoxyphenyl)penta-1,4-dien-3-one as a yellow powder (yield: 20.0 g; 86.0% of theory).

[0083] Step 3: The reaction was carried out in a manner similar to that of Example 1, except that only 1 mmol of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)penta-1,4-dien-3-one was used, to give the title compound (2) as a cream-colored powder (yield: 0.75 g; 87.0% of theory).

[0084] 1 H-NMR: δ H (300 MHz, MeOD) 6.94 (1 H, s, (C6, C12)), 6.85 (1 H, s, (C6 m , C12 m )), 6.73 (2 H, d, J 1.1, (C3, C4, C8, C9)), 6.69-6.63 (2 H, m, (C3 m , C4 m , C8 m , C9 m )), 4.34-4.27 (1 H, m, (C13, C18)), 4.26-4.17 (1 H, m, (C13) m , C18 m)), 3.99-3.87 (4 H, m, (C14, C16)), 3.78 (2 H, s, (C20, C22)), 3.73 (4 H, s (C20 m , C22 m )), 3.36-3.12 (4 H, m (C14, C16)), 1.84-1.67 (4 H, m (C34, C46)), 1.52-1.41 (4 H, m (C35, C47)), 1.41-1.24 (33 H, m), 0.89 (6 H, t, J 6.8 (C44, C56)). 13 C-NMR: δ C (75 MHz, MeOD) 207.4 (C15 m ), 206.8 (C15), 150.2 (C1, C11), 150.1 (C1 m , C11 m ), 149.4 (C2, C10), 149.3 (C2 m , C10 m ), 130.4 (C5, C7), 130.3 (C5 m , C7 m ), 123.0 (C4, C8), 122.4 (C4 m , C8 m )), 114.8 (C6, C12), 114.0 (C3, C9), 113.9 (C3 m , C9 m ), 70.2 (C33, C45), 70.1 (C33 m , C45 m ), 62.6 (C13 m , C18 m ), 62.3 (C13, C18), 56.4 (C20, C22), 56.3 (C20 m , C22 m ), 46.6 (C14 m , C16 m), 46.0 (C14, C16), 33.1 (C34, C42), 30.8 (C35, C36, C47, C48), 30.7 (C37, C38, C49, C50), 30.6 (C39, C51), 30.5 (C40, C52), 27.3 (C41, C53), 27.2 (C42, C54), 23.8 (C43, C55), 14.5 (C44, C56). Elemental Analysis: Expected: C, 59.97; H, 8.90; N, 3.25; S, 7.45 Found: C, 59.15; H, 8.92; N, 3.22; S, 7.13 HRMS: (ESI + , m / z) C 43 H 77 N 2 O 11 S 2 [M+H] + Calculated value: 861.495738; Measured value: 861.495738.

[0085] Example 3 Preparation of 1,5-bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (3)

[0086] [ka]

[0087] Step 1: The reaction was carried out in a manner similar to that of Example 1, except that 1-bromotetradecane was used instead of 1-bromooctane, to give 3-methoxy-4-tetradecyloxybenzaldehyde as a cream-colored powder (yield: 12.1 g; 99.2% of theory).

[0088] Step 2: The reaction was carried out in a manner similar to that of Example 1, except that the crude product was washed with MeOH and then recrystallized from boiling heptane to give 1,5-bis(3-methoxy-4-tetradecyloxyphenyl)penta-1,4-dien-3-one as a yellow powder (yield: 1.17 g; 46.4% of theory).

[0089] Step 3: The reaction was carried out in a similar manner to Example 2 to give the title compound (3) as a cream-colored powder (yield: 0.72 g; 78.3% of theory).

[0090] 1 H-NMR: δ H (300 MHz, MeOD) 6.97 (1 H, s (C6, C12)), 6.88 (1 H, s (C6 m , C12 m )), 6.79-6.74 (2 H, m (C3, C4, C8, C9)), 6.74-6.62 (2 H, m (C3 m , C4 m , C8 m , C9 m )), 4.39-4.29 (1 H, m (C13, C18)), 4.28-4.20 (1 H, m (C13) m , C18 m )), 4.02-3.89 (4 H, m, (C33, C47)), 3.81 (3 H, s (C20, C22)), 3.76 (3 H, s (C20 m , C22 m )), 3.36-3.16 (4 H, m (C14, C16)), 1.87-1.72 (4 H, m (C34, C48)), 1.55-1.46 (4 H, m (C35, C49)), 1.42-1.25 (42 H, m (C36-C45, C50-C59)), 0.92 (6 H, t, J 6.9 (C46, C60)). 13 C-NMR: δ C (75 MHz, MeOD) 207.4 (C15 m), 206.9 (C15), 150.2 (C1, C11), 150.1 (C1 m , C11 m ), 149.4 (C2, C10), 149.3 (C2 m , C10 m )), 130.4 (C5, C7), 130.3 (C5 m , C7 m ), 123.0 (C4, C8), 122.4 (C4 m , C8 m ), 114.8 (C6, C12), 114.0 (C3, C9), 113.8 (C3 m , C9 m )), 70.2 (C33, C47), 70.1 (C33 m , C47 m ), 62.6 (C13 m , C18 m ), 62.3 (C13, C18), 56.4 (C20, C22), 56.3 (C20 m , C22 m ), 46.6 (C14 m , C16 m ), 46.0 (C14, C16), 33.1 (C34, C48), 31.0-30.3 (m) (C35-C42, C49-C56), 27.3 (C43, C57), 27.2 (C44, C58), 23.8 (C45, C59), 14.5 (C46, C60). Elemental analysis: Expected: C, 61.54; H, 9.23; N, 3.05; S, 6.99 Found: C, 59.58; H, 9.32; N, 2.93; S, 6.22 HRMS: (ESI - , m / z) C 47 H 85 N 2 O 11 S 2 [M+H] + Calculated value: 917.558929; Measured value: 917.557029.

[0091] Example 4 Preparation of 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (4)

[0092] [ka]

[0093] Step 1: The reaction was carried out in a manner similar to that of Example 1, except that 1-bromohexadecane was used instead of 1-bromooctane, to give 4-hexadecyloxy-3-methoxybenzaldehyde as a cream-colored powder (yield: 13.0 g; 98.7% of theory).

[0094] Steps 2 & 3 (one-pot synthesis): 4-Hexadecyloxy-3-methoxybenzaldehyde (2.63 g, 7 mmol) was dissolved in 14 mL of isopropanol with lithium hydroxide monohydrate (LiOH.H) as catalyst. 2 The mixture was reacted with acetone (0.20 g, 3.5 mmol) in the presence of 2,4-dimethylformamide (14.7 g, 0.35 mmol) at 45 °C for 12 h. It was then treated with triethylamine (0.07 g, 0.7 mmol), 10.5 mL of ammonium hydrogen sulfite NH 4 HSO 3 A 1M aqueous solution of 1M HCl and an additional 38.5 mL of isopropanol were added, after which the reaction mixture was refluxed with vigorous stirring for 14 h. The reaction mixture was then refluxed with 0.25 mL of HCl using a balloon filled with oxygen gas to oxidize the unreacted sulfite to sulfate. 2 The mixture was placed under atmospheric pressure. 50 mL of pentane was then added and water was distilled off as an azeotrope using a Dean-Stark apparatus at 50° C. The liquid residue was then concentrated under reduced pressure on a rotary evaporator. Acetone was added to the resulting residue and extracted using a Soxhlet extractor. Inorganic salts were removed by washing with MeOH, and then the remaining residue was stripped of solvent on a rotary evaporator and the residue was thoroughly dried in a vacuum desiccator to give the title compound (4) as a cream-colored powder (yield: 2.17 g; 63.8% of theory).

[0095] 1 H-NMR: δ H (300 MHz, MeOD) 6.94 (s, 1H, C6, C12), 6.85 (d, J = 1.7 Hz, 1H, (C6 m , C12 m )), 6.73 (d, J = 1.1 Hz, 1H, (C3, C4, C8, C9)), 6.65 (d, J = 2.3 Hz, 3H, (C3 m , C4 m , C8 m , C9 m )), 4.31 (dd, J = 9.3, 5.2 Hz, 1H, (C13, C18)), 4.22 (dd, J = 10.4, 4.0 Hz, 1H, (C13 m , C18 m )), 3.94 (t, J = 6.6, 6.6 Hz, 4H (C33, C49)), 3.78 (s, 2H (C20, C22), 3.74 (s, 4H (C20) m , C22 m )), 1.76 (s, 4H (C34, C50)), 1.29 (s, 44H(C35-C47, C51-C63), 0.89 (t, J = 6.8 Hz, 7H (C48, C64) Elemental analysis: Expected values: C, 62.93; H, 9.53; N, 2.88; S, 6.59 Measurements: C, 58.93; H, 9.50; N, 2.77; S, 6.19.

[0096] Example 5 Preparation of 1,5-bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (5)

[0097] [ka]

[0098] Step 1: The reaction was carried out in a manner similar to that of Example 1, except that 1-bromooctadecane was used instead of 1-bromooctane, and 10 times the volume of the solution was used, to give 3-methoxy-4-octadecyloxybenzaldehyde as a cream-colored powder (yield: 1.38 g; 97.6% of theory).

[0099] Steps 2 & 3 (one-pot synthesis): The reaction was carried out in a manner similar to that of Example 4 using 3-methoxy-4-octadecyloxybenzaldehyde instead of 4-hexadecyloxy-3-methoxybenzaldehyde to give the title compound (5) as a cream-colored powder (yield: 11.9 g; 33.0% of theory).

[0100] 1 H-NMR (300 MHz, MeOD) δ 6.94 (s, 1H), 6.85 (d, J = 1.6 Hz, 1H), 6.75-6.70 (m, 2H), 6.65 (d, J = 2.5 Hz, 2H), 4.32 (dd, J = 9.3, 5.2 Hz, 1H), 4.22 (dd, J = 10.3, 4.1 Hz, 1H), 3.94 (t, J = 6.6, 6.6 Hz, 4H), 3.79 (s, 3H), 3.74 (s, 3H), 1.82-1.72 (m, 5H), 1.54-1.22 (m, 62H), 0.88 (t, J = 7.0 Hz, 6H).

[0101] Example 6 Preparation of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (6)

[0102] [ka]

[0103] Step 1: The synthesis and production were the same as in Example 2.

[0104] Steps 2 & 3 (one-pot synthesis): 4-Dodecyloxy-3-methoxybenzaldehyde was used instead of 4-hexadecyloxy-3-methoxybenzaldehyde, and ammonium hydrogen sulfite NH was used as the sulfonating agent. 4 HSO 3 The reaction was carried out in a similar manner to Example 4, except that sodium hydrogen sulfite NaHSO3 was used instead of , to give the title compound (6) as a cream-colored powder (yield: 1.70 g; 55.7% of theory).

[0105] 1 H-NMR (300 MHz, MeOD) 6.95 (s, 1H), 6.85 (s, 1H), 6.77-6.71 (m, 2H), 6.65 (d, J = 2.0 Hz, 2H), 4.31 (dd, J = 8.6, 5.8 Hz, 1H), 4.22 (dd, J = 10.3, 4.1 Hz, 1H), 3.99-3.85 (m, 4H), 3.79 (s, 3H), 3.74 (s, 3H), 1.84-1.69 (m, 4H), 1.55-1.41 (m, 4H), 1.41-1.21 (m, 42H), 0.88 (t, J = 7.0 Hz, 6H).

[0106] Example 7 Preparation of 1,5-bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (7)

[0107] [ka]

[0108] Step 1: The synthesis and production were the same as in Example 3.

[0109] Steps 2 & 3 (one-pot synthesis): 3-Methoxy-4-tetradecyloxybenzaldehyde was used instead of 4-hexadecyloxy-3-methoxybenzaldehyde, and ammonium hydrogen sulfite NH was used as the sulfonating agent. 4 HSO 3 Instead of sodium hydrogen sulfite (NaHSO) 3 The reaction was carried out in a similar manner to that in Example 4, except that the following was used to give the title compound (6) as a cream-colored powder (yield: 1.70 g; 55.7% of theory).

[0110] 1 H NMR (300 MHz, MeOD) δ 6.95 (s, 1H), 6.86 (d, J = 1.5 Hz, 2H), 6.74 (s, 2H), 6.66 (d, J = 1.8 Hz, 3H), 4.32 (dd, J = 9.6, 4.8 Hz, 1H), 4.24 (dd, J = 10.4, 3.9 Hz, 2H), 3.94 (d, J = 7.0 Hz, 4H), 3.79 (s, 3H), 3.74 (s, 4H), 3.39-3.33 (m, 1H), 3.28-3.14 (m, 2H), 1.84-1.69 (m, 4H), 1.56-1.42 (m, 4H), 1.41-1.20 (m, 44H), 0.91 (t, J = 6.3, 6.3 Hz, 6H). HRMS: (ESI - , m / z) C 47 H 77 N 2 O 11 S 2 [M+H] + Calculated value: 927.469721; Measured value: 927.469727.

[0111] Example 8 Preparation of 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (8)

[0112] [ka]

[0113] Step 1: The synthesis and production were the same as in Example 4.

[0114] Steps 2 & 3 (one-pot synthesis): As a sulfonating agent, ammonium hydrogen sulfite NH 4 HSO 3 Instead of sodium hydrogen sulfite (NaHSO) 3 The reaction was carried out in a similar manner to Example 4, except that the following was used, to give the title compound (8) as a cream-colored powder (yield: 2.66 g; 77.3% of theory).

[0115] 1 H-NMR: δ H (700 MHz, MeOD) δ 6.96 (s, 1H), 6.88 (d, J = 1.8 Hz, 1H), 6.75 (d, J = 1.2 Hz, 1H), 6.70-6.65 (m, 3H), 4.34 (dd, J = 10.3, 4.2 Hz, 1H), 4.25 (dd, J = 10.8, 3.7 Hz, 1H), 3.96 (t, J = 6.5 Hz, 4H), 3.80 (s, 2H), 3.76 (s, 4H), 3.36-3.33 (m, 1H), 3.31-3.20 (m, 2H), 1.78 (dt, J = 8.7, 6.7 Hz, 4H), 1.49 (td, J = 8.0, 7.6, 4.2 Hz, 4H), 1.42-1.36 (m, 5H), 1.35-1.28 (m, 49H), 0.91 (t, J = 7.0 Hz, 5H). 13 C-NMR: δ C(75 MHz, MeOD) (176 MHz, MeOD) δ 207.5, 207.0, 150.2, 150.1, 149.4, 149.3, 130.4, 130.3, 123.1, 122.4, 114.8, 114.0, 113.9, 70.2, 70.1, 62.6, 62.3, 46.6, 46.0, 33.1 (d, J = 2.1 Hz), 30.9, 30.8, 30.8, 30.8, 30.8, 30.7, 30.6, 30.6, 30.5-30.4 (m), 27.3, 27.2, 23.8, 14.5. Elemental Analysis: Expected: C, 62.30; H, 8.61; Na, 4.68; S, 6.52 Found: C, 60.68; H, 9.07; S, 5.49 HRMS: (ESI + , m / z) C 51 H 85 Na 2 O 11 S 2 [M+H] + Calculated value: 983.532321 Measured value: 983.531847.

[0116] Example 9 Preparation of 1,5-bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (9)

[0117] [ka]

[0118] Step 1: The synthesis and production were the same as in Example 5.

[0119] Steps 2 & 3 (one-pot synthesis): The reaction was carried out in a similar manner to Example 8, except that 3-methoxy-4-octadecyloxybenzaldehyde was used instead of 4-hexadecyloxy-3-methoxybenzaldehyde, to give the title compound (9) as a cream-colored powder (yield: 1.05 g; 28.9% of theory).

[0120] 1 H-NMR: δ H (300 MHz, MeOD) δ 6.96 (s, 1H), 6.87 (d, J = 1.6 Hz, 1H), 6.78-6.71 (m, 2H), 6.70-6.61 (m, 2H), 4.40-4.26 (m, 1H), 3.96 (dd, J = 7.6, Elemental analysis: Expected values: C, 63.55; H, 8.92; S, 6.17 Measured: C, 59.72; H, 9.06; S, 6.78 HRMS: (ESI + , m / z) C 55 H 93 Na 2 O 11 S 2 [M+H] + Calculated value: 1039.594921 Measured value: 1039.595834.

[0121] Example 10 Preparation of 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid dipotassium salt (10)

[0122] [ka]

[0123] Step 1: The synthesis and production were the same as in Example 4.

[0124] Steps 2 & 3 (one-pot synthesis): As a sulfonating agent, ammonium hydrogen sulfite NH 4 HSO 3 Instead of potassium hydrogen sulfite, KHSO 3 The reaction was carried out in a similar manner to Example 4, except that the following was used to give the title compound (10) as a cream-colored powder (yield: 1.16 g; 32.8% of theory).

[0125] 1 H-NMR: δ H (300 MHz, MeOD) 6.94 (s, 1H, C6, C12), 6.85 (d, J = 1.7 Hz, 1H, (C6 m , C12 m )), 6.73 (d, J = 1.1 Hz, 1H, (C3, C4, C8, C9)), 6.65 (d, J = 2.3 Hz, 3H, (C3 m , C4 m , C8 m , C9 m )), 4.31 (dd, J = 9.3, 5.2 Hz, 1H, (C13, C18)), 4.22 (dd, J = 10.4, 4.0 Hz, 1H, (C13 m , C18 m )), 3.94 (t, J = 6.6, 6.6 Hz, 4H (C33, C49)), 3.78 (s, 2H (C20, C22), 3.74 (s, 4H (C20) m , C22 m )), 1.76 (s, 4H (C34, C50)), 1.29 (s, 44H(C35-C47, C51-C63), 0.89 (t, J = 6.8 Hz, 7H (C48, C64) Elemental analysis: Expected values: C, 60.32; H, 8.34; K, 7.70; S, 6.31 Measured value: C, 56.57; H, 8.62; S, 8.00 HRMS: (ESI + , m / z) C 51 H 85 K 2 O 11 S2 [M+H] + Calculated value: 1015.480195 Measured value: 1015.480682.

[0126] Example 11 Preparation of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid dicholine salt (11)

[0127] [ka]

[0128] Step 1: The synthesis and production were the same as in Example 2.

[0129] Step 2: The synthesis and production were the same as in Example 2.

[0130] Step 3: Using only 0.5 mmol of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)penta-1,4-dien-3-one and after passing through an ion exchange resin, NH 4 The reaction was carried out in a similar manner to Example 1, variant 3.1, except that a small excess of aqueous choline hydroxide solution was added instead of the OH solution, to give the title compound (11) as a cream-colored powder (yield: 0.52 g; 100.7% of theory).

[0131] 1 H-NMR: δ H(300 MHz, MeOD) 6.95 (d, J = 1.2 Hz, 1H), 6.86 (d, J = 1.6 Hz, 1H), 6.75 (d, J = 1.1 Hz, 2H), 6.66 (d, J = 2.4 Hz, 2H), 4.31 (dd, J = 9.2, 5.1 Hz, 1H), 4.22 (dd, J = 10.3, 4.1 Hz, 1H), 4.01-3.89 (m, 8H), 3.79 (s, 3H), 3.74 (s, 3H), 3.48-3.39 (m, 4H), 3.16 (s, 20H), 1.82-1.69 (m, 4H), 1.29 (q, J = 5.2, 5.2, 4.2 Hz, 35H), 0.89 (d, J = 6.9 Hz, 6H). 13 C-NMR: δ C (75 MHz, MeOD) 207.4, 206.9, 150.2, 150.1, 149.4, 149.3, 130.6, 130.4, 123.1, 122.5, 114.8, 114.1, 113.9, 70.2, 70.1, 69.1-68.9 (m), 62.3, 57.1, 56.5, 56.4, 54.8-54.5 (m), 46.6, 46.0, 33.1, 31.0-30.4 (m), 27.3, 27.2, 23.8, 14.5. Elemental analysis: Expected: C, 61.48; H, 9.54; N, 2.71; S, 6.19 Measurements: C, 58.31; H, 9.56; N, 3.34; S, 6.02.

[0132] Example 12 Preparation of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid bis(triethanolammonium) salt (12)

[0133] [ka]

[0134] Step 1: The synthesis and production were the same as in Example 2.

[0135] Step 2: The synthesis and production were the same as in Example 2.

[0136] Step 3: Using only 0.5 mmol of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)penta-1,4-dien-3-one and after passing through an ion exchange resin, NH 4 The reaction was carried out in a similar manner to Example 1, variant 3.1, except that a slight excess of aqueous triethanolamine was added instead of the OH solution, to give the title compound (12) as a cream-colored powder (yield: 0.55 g; 98.5% of theory).

[0137] 1 H-NMR: δ H (300 MHz, MeOD) 7.0 (s, 1H), 6.9 (d, J = 1.6 Hz, 1H), 6.7 (d, J = 1.1 Hz, 2H), 6.7 (d, J = 2.1 Hz, 2H), 4.4-4.3 (m, 1H), 4.3-4.2 (m, 1H), 3.9 (t, J = 6.6, 6.6, 1.6 Hz, 4H), 3.9-3.8 (m, 14H), 3.8 (s, 3H), 3.7 (s, 3H), 3.4 (q, J = 5.2, 5.2, 5.0 Hz, 12H), 1.8-1.7 (m, 4H), 1.5-1.4 (m, 4H), 1.4-1.2 (m, 34H), 0.9-0.9 (m, 6H). 13 C-NMR: δ C(75 MHz, MeOD) 207.4, 206.9, 150.2, 150.1, 149.3, 130.5, 130.3, 123.1, 122.4, 114.8, 114.0, 113.8, 70.2, 70.1, 62.6, 56.9, 56.7, 56.4, 56.3, 46.6, 33.1, 30.8, 30.8, 30.7, 30.5, 27.3, 27.2, 23.8, 14.5. Elemental Analysis: Expected: C, 58.80; H, 8.79; N, 2.49; S, 5.71 Found: C, 57.01; H, 9.21; N, 2.71; S, 5.29.

[0138] Example 13 Preparation of 1,1'-(2-oxocyclopentane-1,3-diyl)-bis[(3-methoxy-4-octyloxyphenyl)methanesulfonic acid ammonium salt] (13)

[0139] [ka]

[0140] Step 1: The synthesis and production were the same as in Example 1.

[0141] Step 2: The reaction was carried out in a manner similar to that of Example 1, except that 4-octyloxy-3-methoxybenzaldehyde was reacted with cyclopentanone (0.29 g, 3.5 mmol) instead of acetone, and the crude product precipitate was washed with hexane instead of MeOH after centrifugation, to give 2,5-bis(3-methoxy-4-octyloxybenzylidene)cyclopentan-1-one as a yellow powder (yield: 178 g; 87.9% of theory).

[0142] Step 3: 2,5-Bis(3-methoxy-4-octyloxybenzylidene)cyclopentan-1-one (0.29 g, 0.5 mmol) was dissolved in 6.2 mL of sulfurous acid in the presence of triethylamine (0.59 g, 10 mmol). 2 SO 3 The reaction was carried out in a similar manner to Example 1, variant 3.1, except that the reaction was carried out with a 0.8 M aqueous solution of to give the title compound (13) in the form of yellowish crystals (yield: 0.37 g; 96.1% of theory).

[0143] 1 H-NMR: δ H (300 MHz, MeOD) 7.19-7.03 (m, 2H), 6.98-6.74 (m, 3H), 6.48-6.32 (m, 1H), 4.63-4.37 (m, 2H), 4.07-3.84 (m, 5H), 3.83-3.67 (m, 6H), 3.39-3.31 (m, 2H), 3.23 (d, J = 7.9 Hz, 1H), 2.61 (d, J = 30.9 Hz, 1H), 2.53 (s, 1H), 2.35 (q, J = 11.3, 9.5 Hz, 1H), 1.91 (ddd, J = 11.7, 8.2, 3.7 Hz, 1H), 1.86-1.70 (m, 4H), 1.60-1.39 (m, 6H), 1.37-1.23 (m, 16H), 0.94-0.86 (m, 6H). 13 C-NMR: δ C(75 MHz, MeOD) 215.8, 148.8, 148.6, 147.9, 130.5, 127.3, 126.5, 122.9, 122.0, 114.4, 113.6, 113.3, 112.5, 111.8, 68.8, 68.7, 68.4, 64.7, 64.3, 63.9, 55.0, 54.8, 53.4, 51.4, 49.6, 47.3, 47.0, 46.7, 31.7, 31.6, 31.6, 29.3, 29.1, 29.0, 29.0, 29.0, 28.9, 25.9, 25.7, 23.3, 22.4, 22.3, 13.0. Elemental Analysis: Expected: C, 57.34; H, 8.06; N, 3.61; S, 8.27; Found: C, 57.34; H, 8.50; N, 4.50; S, 6.85 HRMS: (ESI + , m / z) C 37 H 63 N 2 O 11 S 2 [M+H] + Calculated value: 775.386779; Measured value: 775.385622.

[0144] Since this compound contains four stereocenters and the product represents a diastereomeric mixture, precise assignment of peaks in the NMR spectrum was not possible.

[0145] Example 14 Testing isolated sulfonate compounds according to formula (I) and (II) for their suitability as surfactants

[0146] As usual, the critical micelle concentration (CMC), i.e. the concentration at which micelles can be formed, was measured as a parameter of the surface active properties of the new sulfonate compounds using a K100C force tensiometer from Kruss Scientific, according to the Wilhelmy plate method, at 25° C. and natural pH. For comparison, dodecyldimethylamine sulfonate ("Comparative") was measured under the same conditions. For comparison, dodecyldimethylamine N-oxide ("C1") was measured under the same conditions. The results are shown in Table 1 below. The lower the value, the stronger the surfactant effect of the respective substance.

[0147] [Table 1]

[0148] It can be seen that the three tested examples according to the invention show CMC values ​​that are lower, and in the majority significantly lower, than the comparative substances used in many commercial products. 1 Therefore, among the three compounds according to the invention, the radical R 1 Or R 5 The CMC value of 0.32 g / l for disulfonate (1) from Example 1, which has the lowest number of carbon atoms, is still less than half that of the comparative commercial surfactant.

[0149] Due to analogies or high similarities in the substitution patterns of other compounds according to the invention that have not yet been tested, one skilled in the art may expect that a strong surfactant effect will also be consistently detectable for these compounds. This is equally true for the substances (1)-(13) synthesized herein based on vanillin, as well as for any other compounds that can be produced according to the present invention using similar lignin degradation products as starting materials. In particular, most of them have a higher concentration of the radical R compared to vanillin. 3 The radical R 1 Or R 5This is because it has more carbon atoms.

[0150] Thus, the present invention provides a class of novel sulfonate compounds, most of which are suitable for use as surfactants, which can be obtained in an economical and environmentally friendly manner by relatively simple synthetic steps.

Claims

1. The following formula (I) or (II): 【Chemical 1】 [In the formula, Each R １ is selected from linear, branched or cyclic hydrocarbon radicals having 4 to 26 carbon atoms, wherein optionally at least one carbon atom is replaced by an oxygen or sulfur atom; R ２ Or R ５ are each independently selected from hydrogen and a linear, branched or cyclic hydrocarbon radical having 1 to 26 carbon atoms, optionally wherein at least one carbon atom is replaced by an oxygen or sulfur atom; Each R ６ are independently selected from hydrogen and saturated hydrocarbon radicals having 1 to 6 carbon atoms, where optionally two radicals R ６ may be connected, as shown by the dashed line, to form a 5- or 6-membered ring containing the carbonyl carbon atom; and Each X is independently H ＋ monovalent or polyvalent cation X containing ｎ＋ wherein n is ≧1, and wherein in formula (I), optionally both X's together may represent a multivalent cation. Sulfonate compounds by.

2. Each R １ But C ６ -C ２２ represents alkyl; and / or R ２ and R ３ are each independently hydrogen, C １ -C ２２ Alkyl and C １ -C ２２ alkoxy; and / or R ４ and R ５ is selected from hydrogen, methyl and methoxy; and / or Each R ６ is selected from hydrogen, methyl and ethyl; and / or Each X is H ＋ , Na ＋ , K. ＋ , N.H. ４ ＋ or an organic ammonium ion, 2. The sulfonate compound of claim 1, wherein:

3. R １ But C ８ -C １８ represents alkyl; and / or R ２ and R ３ are each independently hydrogen, C １ -C ４ Alkyl and C １ -C ４ alkoxy; and / or R ４ and R ５ are hydrogen, respectively.

3. The sulfonate compound according to claim 1 or 2, characterized in that:

4. Both R １ But the same C ８ -C １８ represents an alkyl radical; R ２ and R ３ one of which is hydrogen and the other is methoxy, or both of which are methoxy; R ４ and R ５ are each hydrogen; Both radicals R ６ are hydrogen or methyl, or are joined to form an ethylene or propylene radical, thus forming a 5- or 6-membered ring containing the carbonyl carbon atom; and Each X is H ＋ , Na ＋ , N.H. ４ ＋ or an organic ammonium ion, which may optionally be (2-hydroxyethyl)trimethylammonium (choline) or triethanolammonium; 3. The sulfonate compound according to claim 1 or 2, characterized in that:

5. The following compounds: 1,5-bis(3-methoxy-4-octyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (1) 【Chemistry 2】 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (2) 【Chemistry 3】 1,5-bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (3) 【Chemistry 4】 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (4) 【Chemistry 5】 1,5-bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (5) 【Chemistry 6】 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (6) 【Chemistry 7】 1,5-bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (7) 【Chemistry 8】 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (8) 【Chemistry 9】 1,5-bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (9) 【Chemistry 10】 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid dipotassium salt (10) 【Chemistry 11】 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid dicholine salt (11) 【Chemistry 12】 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid bis(triethanolammonium) salt (12) 【Chemistry 13】 1,1'-(2-oxocyclopentane-1,3-diyl)-bis[(3-methoxy-4-octyloxyphenyl)methanesulfonic acid ammonium salt] (13) 【Chemistry 14】 Selected from 3. The sulfonate compound according to claim 1 or 2, characterized in that:

6. 10. A method for producing the sulfonate compound of claim 1, comprising the steps of: 1) In an organic solvent, in the presence of a base, a Williamson etherification reaction is carried out to obtain a compound of the following formula (III): 【Chemistry 15】 [In the formula, R ２ Or R ５ are each independently selected from hydrogen and a linear, branched or cyclic hydrocarbon radical having 1 to 26 carbon atoms, optionally in which at least one carbon atom is replaced by an oxygen or sulfur atom. The 4-hydroxybenzaldehyde derivative according to the formula R １ -Y (wherein, R １ is selected from linear, branched or cyclic hydrocarbon radicals having 4 to 26 carbon atoms, wherein optionally at least one carbon atom may be replaced by an oxygen or sulfur atom, and Y represents a leaving group selected from a halide and a sulfonate, to produce a compound of formula (IV): 【Chemistry 16】 to obtain the corresponding ether by 2) In an organic solvent, using an acidic or basic catalyst, by Claisen-Schmitt double crossed aldol condensation reaction, the ether of formula (IV) is reacted with half an equivalent of acetone or a carboxylic acid of formula (V): 【Chemistry 17】 [In the formula, each R ６ are independently selected from hydrogen and saturated hydrocarbon radicals having 1 to 6 carbon atoms, where optionally two radicals R ６ may be connected, as shown by the dashed line, to form a 5- or 6-membered ring containing the carbonyl carbon atom. to form a compound of formula (VI): 【Chemistry 18】 to obtain the corresponding unsaturated ketone; 3) Reaction of the ketone of formula (VI) with a sulfonating agent in an alcoholic solvent in order to add 1 or 2 equivalents of bisulfite to the double bond of the ketone of formula (VI), optionally followed by ion exchange of the mono- or disulfonate thus obtained and the predetermined counterion X ｎ＋ wherein n is ≧1 to obtain a sulfonate compound according to formula (I) or (II), A method comprising:

7. In step 1), Chloride or bromide is used as the leaving group Y; and / or K ２ CO ３ is used as the base; and / or Acetonitrile is used as the organic solvent.

7. The method according to claim 6, characterized in that:

8. In step 1), bromide is used as the leaving group Y; 2 equivalents of K ２ CO ３ is used as the base, and The reaction is carried out in refluxing acetonitrile.

8. The method according to claim 7, characterized in that:

9. In step 2), Lithium hydroxide monohydrate LiOH.H ２ O is used as the basic catalyst; and / or A lower alcohol, an ether, or a mixture thereof is used as the organic solvent.

7. The method according to claim 6, characterized in that:

10. In step 2), Lithium hydroxide monohydrate LiOH.H in an amount of 1-10 mol % ２ O is used as the basic catalyst, isopropanol is used as the organic solvent; and The reaction is carried out at 40-50°C.

10. The method according to claim 9, characterized in that

11. In step 3), Bisulfite or disulfite is used as the sulfonating agent; and / or a mixture of lower alcohol and water is used as the alcohol solvent; and / or An amine is used as a catalyst.

7. The method according to claim 6, characterized in that:

12. In step 3), Sodium disulfite ２ S ２ O ５ , calcium hydrogen sulfite Ca(HSO ３ ) ２ , ammonium bisulfite NH ４ HSO ３ or trimethylammonium sulfite [(CH ３ ) ３ N] ２ SO ３ is used as the sulfonating agent, Triethylamine, triethanolamine or choline hydroxide is used as the catalyst, and Aqueous methanol or isopropanol is used as the alcohol solvent.

12. The method according to claim 11, characterized by:

13. In step 3), Bisulfite or disulfite is used in an amount of 3 equivalents of bisulfite, respectively, based on the ketone of formula (VI), and the amine catalyst is used in an amount of at least 20 mol % to obtain a disulfonate compound according to formula (I); and Refluxing aqueous isopropanol is used as the alcohol solvent.

13. The method according to claim 12, characterized in that:

14. a) In step 3), in order to convert the sulfonate groups into free sulfonic acid groups, the resulting sulfonate adduct is first subjected to ion exchange using an acidic ion exchange resin and water elution, whereby optionally a predetermined counterion X ｎ＋ to obtain a sulfonate compound according to formula (I) or (II); and / or b) steps 2) and 3) are carried out as a one-pot synthesis; 7. The method according to claim 6, characterized in that:

15. Use of a disulfonate compound of formula (I) or (II) as claimed in claim 1 or 2 or prepared according to claim 6 as a surfactant, wherein the radical R １ Or R ５ wherein the total number of carbon atoms is at least 9.

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