SULFONATE COMPOUNDS

Abstract

Sulfonate compounds according to formula (I) or (II), a preparation method, and their use as surfactants are provided.

##STR00001##

Each R.sup.1 is selected from hydrocarbon radicals having 4 to 26 C atoms and optionally at least one O or S atom; R.sup.2 to R.sup.5 are each independently selected from hydrogen and hydrocarbon radicals having 1 to 26 C atoms and optionally at least one O or S atom; each R.sup.6 is independently selected from hydrogen and hydrocarbon radicals having 1 to 6 carbon atoms, optionally the two radicals R.sup.6 may be connected, as indicated by the dashed line, to form a five-or six-membered ring containing the carbonyl carbon atom; and each X is independently selected from mono-or polyvalent cations X.sup.n+, wherein n is 1, including H.sup.+, wherein, in formula (I), optionally both X together may represent a polyvalent cation.

Claims

1. A sulfonate compound according to formula (I) or (II): ##STR00035## wherein each R.sup.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; R.sup.2 to R.sup.5 are each independently selected from hydrogen and linear, branched or cyclic hydrocarbon radicals having 1 to 26 carbon atoms, wherein optionally at least one carbon atom may be replaced by an oxygen or sulfur atom; each R.sup.6 is independently selected from hydrogen and saturated hydrocarbon radicals having 1 to 6 carbon atoms, wherein optionally the two radicals R.sup.6 may be connected, as indicated by the dashed line, to form a five-or six-membered ring comprising the carbonyl carbon atom; and each X is independently selected from mono-or polyvalent cations X.sup.n+, wherein n is 1, including H.sup.+, wherein, in formula (I), optionally both X together may represent a polyvalent cation.

2. The sulfonate compound according to claim 1, wherein each R.sup.1 represents C.sub.6-C.sub.22 alkyl; and/or R.sup.2 and R.sup.3 are each independently selected from hydrogen, C.sub.1-C.sub.22 alkyl and C.sub.1-C.sub.22 alkoxy; and/or R.sup.4 and R.sup.5 are selected from hydrogen, methyl and methoxy; and/or each R.sup.6 is selected from hydrogen, methyl and ethyl; and/or each X represents H.sup.+, Na.sup.+, K.sup.+, NH.sub.4.sup.+or an organic ammonium ion.

3. The sulfonate compound according to claim 1, wherein R.sup.1 represents C.sub.8-C.sub.18 alkyl; and/or R.sup.2 and R.sup.3 are each independently selected from hydrogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.4 alkoxy; R.sup.4 and R.sup.5 each are hydrogen.

4. The sulfonate compound according to claim 1, wherein both R.sup.1 represent the same C.sub.8-C.sub.18 alkyl radical; one of R.sup.2 and R.sup.3 is hydrogen and the other is methoxy or both of them are methoxy; R.sup.4 and R.sup.5 each are hydrogen; both radicals R.sup.6 are hydrogen or methyl, or they are connected to form an ethylene or propylene radical, thus forming a five-or six-membered ring comprising the carbonyl carbon atom; and each X represents H.sup.+, Na.sup.+, NH.sub.4.sup.+ or an organic ammonium ion, which optionally may be (2-hydroxyethyl)trimethylammonium (choline) or triethanolammonium.

5. The sulfonate compound according to claim 1, wherein it is selected from the following compounds: 1,5-bis(3-methoxy-4-octyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (1) ##STR00036## 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (2) ##STR00037## 1,5-bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (3) ##STR00038## 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (4) ##STR00039## 1,5-bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid diammonium salt (5) ##STR00040## 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (6) ##STR00041## 1,5-bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (7) ##STR00042## 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (8) ##STR00043## 1,5-bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic acid disodium salt (9) ##STR00044## 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid dipotassium salt (10) ##STR00045## 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid dicholine salt (11) ##STR00046## 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic acid bis(triethanolammonium) salt (12) ##STR00047## 1,1-(2-oxocyclopentane-1,3-diyl)-bis[(3-methoxy-4-octyloxyphenyl)methanesulfonic ammonium salt] (13) acid ##STR00048##

6. A method for preparing a sulfonate compound according to claim 1 comprising the following steps: 1) reacting a 4-hydroxybenzaldehyde derivative according to the following formula (III): ##STR00049## wherein R.sup.2 to R.sup.5 are each independently selected from hydrogen and linear, branched or cyclic hydrocarbon radicals having 1 to 26 carbon atoms, wherein optionally at least one carbon atom may be replaced by an oxygen or sulfur atom; with a compound of the formula R.sup.1Y, wherein R.sup.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 halides and sulfonates, by means of an etherification reaction according to Williamson in the presence of a base in an organic solvent, resulting in a corresponding ether according to formula (IV): ##STR00050## 2) reacting the ether of formula (IV) with half an equivalent of acetone or an acetone derivative according to formula (V) ##STR00051## wherein each R.sup.6 is independently selected from hydrogen and saturated hydrocarbon radicals having 1 to 6 carbon atoms, wherein optionally the two radicals R.sup.6 may be connected, as indicated by the dashed line, to form a five-or six-membered ring comprising the carbonyl carbon atom, by means of a double, crossed aldol condensation reaction according to Claisen-Schmidt using an acidic or basic catalyst in an organic solvent, resulting in a corresponding unsaturated ketone according to formula (VI): ##STR00052## 3) reacting the ketone of formula (VI) with a sulfonating agent in an alcoholic solvent for adding one or two equivalent(s) of hydrogen sulfite to the double bond(s) of the ketone of formula (VI), optionally followed by an ion exchange of the mono-or disulfonate thus obtained and introduction of predetermined counterions X.sup.n+, wherein n is 1, resulting in the sulfonate compound according to formula (I) or (II).

7. The method according to claim 6, wherein in step 1), chloride or bromide is used as said leaving group Y; and/or K.sub.2CO.sub.3 is used as said base; and/or acetonitrile is used as said organic solvent.

8. The method according to claim 7, wherein in step 1), bromide is used as said leaving group Y, two equivalents of K.sub.2CO.sub.3 are used as said base, and the reaction is carried out in refluxing acetonitrile.

9. The method according to claim 6, wherein in step 2), lithium hydroxide monohydrate, LiOH.H.sub.2O, is used as said basic catalyst; and/or a lower alcohol, an ether, or a mixture thereof, is used as said organic solvent.

10. The method according to claim 9, wherein in step 2), lithium hydroxide monohydrate LiOH.H.sub.2O in an amount of 1-10 mol % is used as said basic catalyst, isopropanol is used as said organic solvent, and the reaction is carried out at 40-50 C.

11. The method according to claim 6, wherein in step 3), a hydrogen sulfite or a disulfite is used as said sulfonating agent; and/or a mixture of a lower alcohol and water is used as said alcoholic solvent; and/or an amine is used as a catalyst.

12. The method according to claim 11, wherein in step 3), sodium disulfite Na.sub.2S.sub.2O.sub.5, calcium hydrogen sulfite Ca(HSO.sub.3).sub.2, ammonium hydrogen sulfite NH.sub.4HSO.sub.3 or trimethylammonium sulfite [(CH.sub.3).sub.3N].sub.2SO.sub.3 is used as said sulfonating agent, triethylamine, triethanolamine or choline hydroxide is used as said catalyst, and aqueous methanol or isopropanol is used as said alcoholic solvent.

13. The method according to claim 12, wherein in step 3), the hydrogen sulfite or disulfite is used in an amount of three equivalents of hydrogen sulfite and the amine catalyst is used an amount of at least 20 mol %, each based on the ketone of formula (VI), to obtain a disulfonate compound according to formula (I), and refluxing aqueous isopropanol is used as said alcoholic solvent.

14. The method according to claim 6, wherein a) in step 3), the sulfonate adduct obtained is first subjected to an ion exchange using an acidic ion exchange resin and water elution, for converting the sulfonate group(s) into the free sulfonic acid group(s), which optionally may be neutralized using an aqueous solution of the hydroxides of predetermined counterions X.sup.n+, to obtain the sulfonate compound according to formula (I) or (II); and/or b) steps 2) and 3) are carried out as a one-pot synthesis.

15. A surfactant comprising a disulfonate compound of formula (I) or (II) according to claim 1, wherein the total number of carbon atoms of the radicals R.sup.1 to R.sup.5 is at least 9.

Description

EXAMPLES

[0046] The present invention will be described in more detail below by way of examples, which, however, should not be construed as limiting the scope of protection. For illustration purposes, vanillin was used as a representative model compound for the common lignin depolymerization products preferred as starting substances in the method according to the invention and converted into the sulfonate compounds according to the invention. Further examples using its methoxy derivative, syringaldehyde, another typical aromatic aldehyde as a degradation product of lignin, are currently the subject of further experiments conducted by the inventors.

##STR00020##

[0047] According to Reaction Scheme A below, vanillin (III) was first etherified with a series of different fatty alkyl halides R.sup.1Y, whereafter the ethers of the formula (IV) thus obtained were each subjected to a double, crossed aldol condensation reaction with half an equivalent of acetone or cyclopentanone (as indicated by the dashed bonds) to obtain doubly unsaturated ketones of the formula (VI), to which hydrogen sulfite was finally added in order to obtain the corresponding sulfonate compound according to the invention. In the last step, to date only two equivalents of hydrogen sulfite were added to both double bonds of the ketone in order to obtain disulfonates according to formula (I). However, it is obvious to the person skilled in the art that corresponding monosulfonates according to formula (II) or mixtures of both can also be obtained in an analogous manner, using only a smaller amount of sulfonating agent, as already mentioned before.

##STR00021##

Example 1

Preparation of 1,5-bis(3-methoxy-4-octyloxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Diammonium Salt (1)

[0048] ##STR00022##

Step 1:

[0049] Vanillin (6.39 g, 42 mmol) was refluxed together with 1-bromooctane (6.76 g, 35 mmol) and oven-dried K.sub.2CO.sub.3 in 100 mL acetonitrile under nitrogen atmosphere for 48 h. The solvent was then removed on a rotary evaporator and the residue obtained was redissolved in 200 mL of a 1:1 mixture of diethyl ether (Et.sub.2O) and petroleum ether (bp: 40-60 C.) and mixed with 50 mL of 0.5 M NaOH and then washed with 50 ml of water. The organic phase was dried over Na.sub.2SO.sub.4, whereafter the solvent was distilled off in vacuo and the residue was completely dried in a vacuum desiccator, giving the alkylated vanillin, 3-methoxy-4-octyloxybenzaldehyde, as a white powder (yield: 9.13 g; 98.7% of theory).

Step 2:

[0050] 4-Octyloxy-3-methoxybenzaldehyde (1.85 g, 7 mmol) was reacted in 14 mL isopropanol at 45 C. for 12 h with acetone (0.20 g, 3.5 mmol) in the presence of lithium hydroxide monohydrate, LiOH.H.sub.2O, (14.7 g, 0.35 mmol) as a catalyst. The solid precipitate was then centrifuged off, washed 3 times with 6 mL MeOH and dried in vacuo, yielding 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).

Step 3:

Variant 3.1

[0051] 1,5-Bis(3-methoxy-4-octyloxyphenyl)penta-1,4-dien-3-one (1.1 g, 2 mmol) in 22 mL of isopropanol was reacted with 6 mL of a 1 M aqueous solution of sodium hydrogen sulfite, NaHSO.sub.3, in the presence of triethylamine (0.04 g, 0.4 mmol) under reflux for 14 h. The solid precipitate was then centrifuged off and washed with MeOH. The combined organic phases were filtered through a 0.2 m syringe filter, concentrated in vacuo and then passed through a bed of freshly activated acid ion exchange resin (DOWEX 50WX8-100) and washed 3 times with 50 ml of water, whereafter concentrated NH.sub.4OH solution was added in slight excess to produce the ammonium salt, which was filtered off and completely dried in a vacuum desiccator to give the title compound (1) as a white solid (yield: 1.34 g; 89.2% d. Th.).

Variant 3.2

[0052] 1,5-Bis(3-methoxy-4-octyloxyphenyl)penta-1,4-dien-3-one (28 mg, 0.05 mmol) was mixed with 0.1 mL of a 1.5 M aqueous solution of sodium hydrogen sulfite, NaHSO.sub.3, and triethylamine (1 mg, 0.01 mmol) using a Teflon-coated stir bar in a microwave tube, which was tightly sealed and heated in a microwave reactor at 140 C. for 45 min. The reaction mixture was then dried in vacuo and the crude sample was dissolved in MeOD for analysis by NMR spectroscopy.

[0053] .sup.1H NMR: .sub.H (700 MHZ, MeOD) 6.97 (d, 1H, (C6, C12)), 6.89 (s, 1H, (C6.sup.m, C12.sup.m)), 6.78 (m, 2H (C3, C4, C8, C9)), 6.70 (m, 2H, (C3.sup.m, C4.sup.m, C8.sup.m, C9.sup.m)), 4.33 (m, 1H, (C13, C18)), 4.26 (m, 1H, (C13.sup.m, C18.sup.m)), 3.96 (m, 4H, (C33, C41)), 3.81 (s, 3H, (C20, C22)), 3.76 (s, 3H, (C20.sup.m, C22.sup.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)). .sup.13C NMR: .sub.C (176 MHz, MeOD) 207.4 (C15.sup.m), 206.8 (C15), 150.3 (C1, C11), 150.1 (C1.sup.m, C11.sup.m), 149.4 (C2, C10), 149.3 (C2.sup.m, C10.sup.m), 130.5 (C5, C7), 130.3 (C5.sup.m, C7.sup.m), 123.0 (C4, C8), 122.5 (C4.sup.m, C8.sup.m), 114.8 (C6, C12), 114.1 (C3, C9), 113.9 (C3.sup.m, C9.sup.m), 70.2 (C33, C41), 70.1 (C33.sup.m, C41.sup.m), 62.6 (C13m, C18.sup.m), 62.3 (C13, C18), 56.4 (C20, C22), 56.3 (C20.sup.m, C22.sup.m), 46.6 (C14.sup.m, C16.sup.m), 46.0 (C14, C16), 33.1 (C34.sup.m, C42.sup.m), 33.0 (C34, C42), 30.6 (C35.sup.m, C43.sup.m), 30.5 (C35, C43), 30.5 (C36, C44), 30.5 (C36.sup.m, C44.sup.m), 30.5 (C37.sup.m, C45.sup.m), 30.4 (C37, C45), 27.2 (C38.sup.m, C46.sup.m), 27.2 (C38, C46), 23.8 (C39.sup.m, C47.sup.m), 23.7 (C39, C47), 14.5 (C40, C48). Elemental Analysis: expected: C, 56.13; H, 8.07; N, 3.74; S, 8.56; found: C, 55.13; H, 8.33; N, 3.63; S, 8.36 HRMS: (ESI.sup.+, m/z) calculated for C.sub.35H.sub.61N.sub.2O.sub.11S.sub.2 [M+H].sup.+: 749.37168; found: 749.370948.

Example 2

Preparation of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Diammonium Salt (2)

[0054] ##STR00023##

Step 1:

[0055] The reaction was carried out in an analogous manner to that in Example 1, except that 1-bromododecane was used instead of 1-bromooctane, giving 4-dodecyloxy-3-methoxybenzaldehyde as a cream-colored powder (yield: 10.85 g; 96.8% of theory).

Step 2:

[0056] The reaction was carried out in an analogous manner to that in Example 1, yielding 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).

Step 3:

[0057] The reaction was carried out in an analogous manner to that in Example 1, except that only 1 mmol of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)penta-1,4-dien-3-one was used, giving the title compound (2) as a cream-colored powder (yield: 0.75 g; 87.0% of theory).

[0058] 1H NMR: .sub.H (300 MHZ, MeOD) 6.94 (1 H, s, (C6, C12)), 6.85 (1 H, s, (C6.sup.m, C12.sup.m)), 6.73 (2 H, d, J 1.1, (C3, C4, C8, C9)), 6.69-6.63 (2 H, m, (C3.sup.m, C4.sup.m, C8.sup.m, C9.sup.m)), 4.34-4.27 (1 H, m, (C13, C18)), 4.26-4.17 (1 H, m, (C13.sup.m, C18.sup.m)), 3.99-3.87 (4 H, m, (C14, C16)), 3.78 (2 H, s, (C20, C22)), 3.73 (4 H, s (C20.sup.m, C22.sup.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, J6.8 (C44, C56)). .sup.13C NMR: .sub.C (75 MHZ, MeOD) 207.4 (C15.sup.m), 206.8 (C15), 150.2 (C1, C11), 150.1 (C1.sup.m, C11.sup.m), 149.4 (C2, C10), 149.3 (C2.sup.m, C10.sup.m), 130.4 (C5, C7), 130.3 (C5.sup.m, C7.sup.m), 123.0 (C4, C8), 122.4 (C4.sup.m, C8.sup.m)), 114.8 (C6, C12), 114.0 (C3, C9), 113.9 (C3.sup.m, C9.sup.m), 70.2 (C33, C45), 70.1 (C33.sup.m, C45.sup.m), 62.6 (C13.sup.m, C18.sup.m), 62.3 (C13, C18), 56.4 (C20, C22), 56.3 (C20.sup.m, C22.sup.m), 46.6 (C14.sup.m, C16.sup.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.sup.+, m/z) calculated for C.sub.43H.sub.77N.sub.2O.sub.11S.sub.2 [M+H].sup.+: 861.495738; found: 861.495738.

Example 3

Preparation of 1,5-bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Diammonium Salt (3)

[0059] ##STR00024##

Step 1:

[0060] The reaction was carried out in an analogous manner to that in Example 1, except that 1-bromotetradecane was used instead of 1-bromooctane, giving 3-methoxy-4-tetra-decyloxybenzaldehyde as a cream-colored powder (yield: 12.1 g; 99.2% of theory).

Step 2:

[0061] The reaction was carried out in an analogous manner to that in Example 1, except that the crude product was recrystallized from boiling heptane after washing with MeOH, giving 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).

Step 3:

[0062] The reaction was carried out in an analogous manner to that in Example 2, giving the title compound (3) as a cream-colored powder (yield: 0.72 g; 78.3% of theory).

[0063] .sup.1H NMR: .sub.H (300 MHZ, MeOD) 6.97 (1 H, s (C6, C12)), 6.88 (1 H, s (C6.sup.m, C12.sup.m)), 6.79-6.74 (2 H, m (C3, C4, C8, C9)), 6.74-6.62 (2 H, m (C3.sup.m, C4.sup.m, C8.sup.m, C9.sup.m)), 4.39-4.29 (1 H, m (C13, C18)), 4.28-4.20 (1 H, m (C13.sup.m, C18.sup.m)), 4.02-3.89 (4 H, m, (C33, C47)), 3.81 (3 H, s (C20, C22)), 3.76 (3 H, s (C20.sup.m, C22.sup.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, J6.9 (C46, C60)). .sup.13C NMR: .sub.C (75 MHZ, MeOD) 207.4 (C15.sup.m), 206.9 (C15), 150.2 (C1, C11), 150.1 (C1.sup.m, C11.sup.m), 149.4 (C2, C10), 149.3 (C2.sup.m, C10.sup.m)), 130.4 (C5, C7), 130.3 (C5.sup.m, C7.sup.m), 123.0 (C4, C8), 122.4 (C4.sup.m, C8.sup.m), 114.8 (C6, C12), 114.0 (C3, C9), 113.8 (C3.sup.m, C9.sup.m)), 70.2 (C33, C47), 70.1 (C33.sup.m, C47.sup.m), 62.6 (C13.sup.m, C18.sup.m), 62.3 (C13, C18), 56.4 (C20, C22), 56.3 (C20.sup.m, C22.sup.m), 46.6 (C14.sup.m, C16.sup.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.sup., m/z) calculated for C.sub.47H.sub.85N.sub.2O.sub.11S.sub.2 [M+H].sup.+: 917.558929; found: 917.557029.

Example 4

Preparation of 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentane-disulfonic Acid Diammonium Salt (4)

[0064] ##STR00025##

Step 1:

[0065] The reaction was carried out in an analogous manner to that in Example 1, except that 1-bromohexadecane was used instead of 1-bromooctane, giving 4-hexadecyloxy-3-methoxybenzaldehyde as a cream-colored powder (yield: 13.0 g; 98.7% of theory).

Steps 2 & 3 (One-Pot Synthesis):

[0066] 4-Hexadecyloxy-3-methoxybenzaldehyde (2.63 g, 7 mmol) was reacted in 14 mL isopropanol with acetone (0.20 g, 3.5 mmol) in the presence of lithium hydroxide monohydrate, LiOH. H.sub.2O, (14.7 g, 0.35 mmol) as a catalyst at 45 C. for 12 h. Triethylamine (0.07 g, 0.7 mmol), 10.5 mL of a 1 M aqueous solution of ammonium hydrogen sulfite, NH.sub.4HSO.sub.3, and further 38.5 mL of isopropanol were then added, whereafter the reaction mixture was refluxed for 14 h with vigorous stirring. The reaction mixture was then placed under an O.sub.2 atmosphere using a balloon filled with oxygen gas in order to oxidize unreacted sulfite to sulfate. 50 mL of pentane were then added and the water was distilled off as an azeotrope using a Dean-Stark apparatus at 50 C., whereafter the liquid residue was concentrated in vacuo 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, whereafter the solvent was removed from the remaining residue on a rotary evaporator and the residue was completely dried in a vacuum desiccator, giving the title compound (4) as a cream-colored powder (yield: 2.17 g; 63.8% of theory).

[0067] 1H NMR: .sub.H (300 MHZ, MeOD) 6.94 (s, 1H, C6, C12), 6.85 (d, J=1.7 Hz, 1H, (C6m, C12.sup.m)), 6.73 (d, J=1.1 Hz, 1H, (C3, C4, C8, C9)), 6.65 (d, J=2.3 Hz, 3H, (C3.sup.m, C4.sup.m, C8.sup.m, C9.sup.m)), 4.31 (dd, J=9.3, 5.2 Hz, 1H, (C13, C18)), 4.22 (dd, J=10.4, 4.0 Hz, 1H, (C13.sup.m, C18.sup.m)), 3.94 (t, J=6.6, 6.6 Hz, 4H (C33, C49)), 3.78 (s, 2H (C20, C22), 3.74 (s, 4H (C20.sup.m, C22.sup.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: C, 62.93; H, 9.53; N, 2.88; S, 6.59 found: C, 58.93; H, 9.50; N, 2.77; S, 6.19.

Example 5

Preparation of 1,5-bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Diammonium Salt (5)

[0068] ##STR00026##

Step 1:

[0069] The reaction was carried out in an analogous manner to that in Example 1, except that 1-bromooctadecane was used instead of 1-bromooctane and 10 times the solution volume was used, giving 3-methoxy-4-octadecyloxybenzaldehyde as a cream-colored powder (yield: 1.38 g; 97.6% of theory).

Steps 2 & 3 (One-Pot Synthesis):

[0070] The reaction was carried out in an analogous manner to that in Example 4 using 3-methoxy-4-octadecyloxybenzaldehyde instead of 4-hexadecyloxy-3-methoxybenzaldehyde, giving the title compound (5) as a cream-colored powder (yield: 11.9 g; 33.0% of theory).

[0071] .sup.1H NMR (300 MHZ, MeOD) 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).

Example 6

Preparation of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Disodium Salt (6)

[0072] ##STR00027##

Step 1:

[0073] The synthesis and the product were identical to Example 2.

Steps 2 & 3 (One-Pot Synthesis):

[0074] The reaction was carried out in an analogous manner to that in Example 4, except that 4-dodecyloxy-3-methoxybenzaldehyde was used instead of 4-hexadecyloxy-3-methoxybenzaldehyde and sodium hydrogen sulfite, NaHSO3, was used as a sulfonating agent instead of ammonium hydrogen sulfite, NH.sub.4HSO.sub.3, giving the title compound (6) as a cream-colored powder (yield: 1.70 g; 55.7% of theory).

[0075] .sup.1H 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).

Example 7

Preparation of 1,5-bis(3-methoxy-4-tetradecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Disodium Salt (7)

[0076] ##STR00028##

Step 1:

[0077] The synthesis and the product were identical to Example 3.

Steps 2 & 3 (One-Pot Synthesis);

[0078] The reaction was carried out analogously to that in Example 4, except that 3-methoxy-4-tetradecyloxybenzaldehyde was used instead of 4-hexadecyloxy-3-methoxybenzaldehyde and sodium hydrogen sulfite, NaHSO.sub.3, was used as a sulfonating agent instead of ammonium hydrogen sulfite, NH.sub.4HSO.sub.3, giving the title compound (6) as a cream-colored powder (yield: 1.70 g; 55.7% of theory).

[0079] .sup.1H NMR (300 MHz, MeOD) 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.sup., m/z) calculated for C.sub.47H.sub.77N.sub.2O.sub.11S.sub.2 [M+H].sup.+: 927.469721; found: 927.469727.

Example 8

Preparation of 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentane-disulfonic Acid Disodium Salt (8)

[0080] ##STR00029##

Step 1:

[0081] The synthesis and the product were identical to Example 4.

Steps 2 & 3 (One-Pot Synthesis):

[0082] The reaction was carried out in an analogous manner to that in Example 4, except that sodium hydrogen sulfite, NaHSO.sub.3, was used as the sulfonating agent instead of ammonium hydrogen sulfite, NH.sub.4HSO.sub.3, giving the title compound (8) as a cream-colored powder (yield: 2.66 g; 77.3% of theory).

[0083] .sup.1H NMR: .sub.H (700 MHZ, MeOD) 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). 13C NMR: .sub.C (75 MHz, MeOD) (176 MHZ, MeOD) 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.sup.+, m/z) calculated for C.sub.51H.sub.85Na.sub.2O.sub.11S.sub.2 [M+H].sup.+: 983.532321 found: 983.531847.

Example 9

Preparation of 1,5-bis(3-methoxy-4-octadecyloxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Disodium Salt (9)

[0084] ##STR00030##

Step 1:

[0085] The synthesis and the product were identical to Example 5.

Steps 2 & 3 (One-Pot Synthesis):

[0086] The reaction was carried out in an analogous manner to that in Example 8, except that 3-methoxy-4-octadecyloxybenzaldehyde was used instead of 4-hexadecyloxy-3-methoxybenzaldehyde, giving the title compound (9) as a cream-colored powder (yield: 1.05 g; 28.9% of theory).

[0087] .sup.1H NMR: .sub.H (300 MHZ, MeOD) 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, 5.5 Hz, 4H), 3.80 (s, 2H), 3.76 (s, 3H), 1.84-1.70 (m, 5H), 1.30 (d, J=3.2 Hz, 56H), 0.96-0.87 (m, 6H). Elemental Analysis: expected: C, 63.55; H, 8.92; S, 6.17 found: C, 59.72; H, 9.06; S, 6.78 HRMS: (ESI.sup.+, m/z) calculated for C.sub.55H.sub.93Na.sub.2O.sub.11S.sub.2 [M+H].sup.+1039.594921 found: 1039.595834.

Example 10

Preparation of 1,5-bis(4-hexadecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Dipotassium Salt (10)

[0088] ##STR00031##

Step 1:

[0089] The synthesis and the product were identical to Example 4.

Steps 2 & 3 (One-Pot Synthesis):

[0090] The reaction was carried out in an analogous manner to that in Example 4, except that potassium hydrogen sulfite, KHSO.sub.3, was used as a sulfonating agent instead of ammonium hydrogen sulfite, NH.sub.4HSO.sub.3, giving the title compound (10) as a cream-colored powder (yield: 1.16 g; 32.8% of theory).

[0091] .sup.1H NMR: .sub.H (300 MHZ, MeOD) 6.94 (s, 1H, C6, C12), 6.85 (d, J=1.7 Hz, 1H, (C6.sup.m, C12.sup.m)), 6.73 (d, J=1.1 Hz, 1H, (C3, C4, C8, C9)), 6.65 (d, J=2.3 Hz, 3H, (C3.sup.m, C4.sup.m, C8.sup.m, C9.sup.m)), 4.31 (dd, J=9.3, 5.2 Hz, 1H, (C13, C18)), 4.22 (dd, J=10.4, 4.0 Hz, 1H, (C13.sup.m, C18.sup.m)), 3.94 (t, J=6.6, 6.6 Hz, 4H (C33, C49)), 3.78 (s, 2H (C20, C22), 3.74 (s, 4H (C20.sup.m, C22.sup.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: C, 60.32; H, 8.34; K, 7.70; S, 6.31 found: C, 56.57; H, 8.62; S, 8.00 HRMS: (ESI.sup.+, m/z) calculated for C.sub.51H.sub.85K.sub.2O.sub.11S.sub.2 [M+H].sup.+: 1015.480195 found: 1015.480682.

Example 11

Preparation of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Dicholine Salt (11)

[0092] ##STR00032##

Step 1:

[0093] The synthesis and the product were identical to Example 2.

Step 2:

[0094] The synthesis and the product were identical to Example 2.

Step 3:

[0095] The reaction was carried out in an analogous manner to that in Example 1, Variant 3.1, except that only 0.5 mmol of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)penta-1,4-dien-3-one were used and that an aqueous solution of choline hydroxide was added in slight excess instead of the NH.sub.4OH solution after passing the ion exchange resin, giving the title compound (11) as a cream-colored powder (yield: 0.52 g; 100.7% of theory).

[0096] .sup.1H NMR: .sub.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). .sup.13C NMR: .sub.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 found: C, 58.31; H, 9.56; N, 3.34; S, 6.02.

Example 12

Preparation of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)-3-oxo-1,5-pentanedisulfonic Acid Bis(triethanolammonium) Salt (12)

[0097] ##STR00033##

Step 1:

[0098] The synthesis and the product were identical to Example 2.

Step 2:

[0099] The synthesis and the product were identical to Example 2.

Step 3:

[0100] The reaction was carried out in an analogous manner to that in Example 1, Variant 3.1, except that only 0.5 mmol of 1,5-bis(4-dodecyloxy-3-methoxyphenyl)penta-1,4-dien-3one were used and that an aqueous solution of triethanolamine was added in slight excess instead of the NH.sub.4OH solution after the passage of the ion exchange resin, giving the title compound (12) as a cream-colored powder (yield: 0.55 g; 98.5% of theory).

[0101] 1H NMR: .sub.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). .sup.13C NMR: .sub.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.

Example 13

Preparation of 1,1-(2-oxocyclopentane-1,3-diyl)-bis[(3-methoxy-4-octyloxyphenyl)methanesulfonic Acid Ammonium Salt] (13)

[0102] ##STR00034##

Step 1:

[0103] The synthesis and the product were identical to Example 1.

Step 2:

[0104] The reaction was carried out in an analogous manner to that in Example 1, except that the 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 centrifuging, giving 2,5-bis(3-methoxy-4-octyloxybenzylidene)cyclopentan-1-one as a yellow powder (yield: 1 78 g; 87.9% of theory).

Step 3:

[0105] The reaction was carried out in an analogous manner to that in Example 1, Variant 3.1, except that 2,5-bis(3-methoxy-4-octyloxybenzylidene)cyclopentan-1-one (0.29 g, 0.5 mmol) was reacted with 6.2 mL of a 0.8 M aqueous solution of sulfurous acid, H.sub.2SO.sub.3, in the presence of triethylamine (0.59 g, 10 mmol), giving the title compound (13) in the form of yellowish crystals (yield: 0.37 g; 96.1% of theory).

[0106] 1H NMR: .sub.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). .sup.13C NMR: .sub.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.sup.+, m/z) calculated for C.sub.37H.sub.63N.sub.2O.sub.11S.sub.2 [M+H].sup.+: 775.386779; found: 775.385622.

[0107] An exact assignation of the peaks in the NMR spectra was not possible since the compound comprises four stereocenters and the product represents a mixture of diastereomers.

Example 14

Tests Regarding the Suitability of the Isolated Sulfonate Compounds According to Formulae (I) and (II) as Surfactants

[0108] As usual, the critical micelle concentration (CMC), i.e. the concentration at which micelles can form, was determined as a parameter for the surfactant properties of the novel sulfonate compounds using a K100C Force Tensiometer from Krss Scientific using the Wilhelmy plate method at 25 C. and natural pH. For comparison, dodecyldimethylamine sulfonate (Comparison) was measured under the same conditions. The results are given in Table 1 below, with lower values indicating a stronger surfactant effect of the respective substance.

TABLE-US-00001 TABLE 1 Compound CMC (mg/L) (1) 3.2 10.sup.2 (2) 64 (3) 34 V1 6.8 10.sup.2

[0109] It can be seen that the three tested examples according to the invention show lowerand in the majority even significantly lowerCMC values than the comparison substance, which is used in a large number of commercially available products. However, the CMC value of 0.32 g/l for the disulfonate (1) from Example 1, which contains the lowest number of carbon atoms in the radicals R.sup.1 to R.sup.5 among the three compounds according to the invention due to the octyl radical R.sup.1, is still less than half of the commercially available surfactant of the comparative example.

[0110] Due to the analogies or high similarities in the substitution patterns of the other compounds according to the invention that have not yet been tested, a person skilled in this art may expect that a strong surfactant effect will also be consistently detectable for these compounds. This applies equally to the substances (1) to (13) synthesized herein based on vanillin as well as to any other compounds that can be produced according to the present invention using similar lignin degradation products as starting materials, especially since the majority of them even have a larger number of carbon atoms in the radicals R.sup.1 to R.sup.5, such as syringaldehyde, which, compared to vanillin, comprises an additional methoxy substituent as the radical R.sup.3.

[0111] The present invention thus provides a group of novel sulfonate compounds which are obtainable by relatively simple synthetic steps in an economical and environmentally friendly manner and the vast majority of which are suitable for use as surfactants.