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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
  • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
  • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
  • C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
  • C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
  • C07C215/50—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
  • C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
  • C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
  • C07C217/58—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
  • C07D211/94—Oxygen atom, e.g. piperidine N-oxide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
  • C07D295/24—Oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/75—Amino oxides

Definitions

• the present invention relates to a process for preparing new amine N-oxide compounds, the compounds thus prepared and their use as surfactants.
• Lignin is an abundant aromatic biopolymer whose structure is mainly based on three substituted phenols called monolignols (p-coumaryl, coniferyl and sinapyl alcohol), which are linked by a variety of different C-O and C-C bonds to create an amorphous 3 -form dimensional structure.
• monolignols p-coumaryl, coniferyl and sinapyl alcohol
• C-O and C-C bonds to create an amorphous 3 -form dimensional structure.
• Different methods have been developed to enable the catalytic degradation of lignin by depolymerization in order to be able to obtain industrially usable monomolecular phenol and/or benzaldehyde derivatives.
• the products of these depolymerization processes can also contain phenolic di-, tri- and oligomers.
• the main products of such depolymerization processes include guaiacol and syringol or vanillin and syringaldehyde, which often each have one or more alkyl and/or alkoxy substituents on the aromatic ring.
• the literature also discloses zwitterionic amine N-oxides for use as surfactants, along with numerous other amphiphilic compounds, typically consisting of hydrophobic hydrocarbons having one or more ionic hydrophilic moieties, such as carboxylic acid, sulfonic acid or quaternary ammonium salts .
• these are almost exclusively N-oxides of fatty amines, i.e. of tertiary alkylamines with 8 or more, at least 12, carbon atoms.
• the aim of the invention was the development of a new synthesis process for the production of aromatic amine N-oxides suitable as surfactants by functionalization of products and similar compounds occurring in large quantities during lignin degradation, preferably in an environmentally friendly manner.
• R 1 from linear, branched or cyclic hydrocarbon radicals with 4 to
• R 2 , R 3 and R 5 are each independently selected from hydrogen, R 1 -O-, R 8 and in formula (I) also from -CH2-N + (O')R 6 R 6 where R 8 represents one linear, branched or cyclic hydrocarbon radical having 1 to 26 carbon atoms, in which at least one carbon atom is optionally replaced by an oxygen or sulfur atom;
• R 4 is selected from hydrogen and R 8 ; and each R 6 group is independently selected from a saturated, linear or branched hydrocarbon group containing from 1 to 6 carbon atoms, optionally in which at least one carbon atom is replaced by a nitrogen, oxygen or sulfur atom; where optionally two radicals R 6 bonded to the same nitrogen atom are connected to one another to form a five- or six-membered nitrogen-containing ring or where optionally one radical R 6 or both radicals R 6 form an amine-N-oxide group -N + (O' )R 6 R 6 are connected to one or both radicals R 6 of such a grouping of another molecule of the formula (I) and forming a bridge * — NN — *
• each R 7 is independently selected from hydrogen, hydroxy and R 8 with a secondary amine HNR 6 R 6 by a Betti/Mannich aminoalkylation reaction in the presence of formaldehyde in a polar solvent, thereby rendering the hydrogen atom ortho to the phenolic OH -group and against- where another substitutable hydrogen atom R 7 of the phenol derivative of the formula (II) is/are replaced by a group -CH2-NR 6 R 6 and a corresponding Betti base of the formula (IV) or (V) is obtained: wherein each R 7 is independently selected from hydrogen, hydroxy, R 8 and in formula (IV) now also from -CH2-NR 6 R 6 ;
• the starting compounds are also easily available products of lignin depolymerization, and the process is carried out in the most environmentally friendly way possible, especially since both the aminoalkylation according to Betti/Mannich and the etherification of the products according to Williamson are characterized by a high atom economy award.
• the Betti/Mannich aminoalkylation in step 1) is carried out in water and more preferably at room temperature, which avoids the use of solvents and large amounts of energy and, surprisingly, the yields can also be increased.
• organic solvents such as alcohols such as methanol, ethanol or (iso)propanol, or acetonitrile or toluene can still be used, and in each case instead of or in a mixture with water.
• the starting compound used is preferably a phenol derivative of the formula (III) which is unsubstituted in the two o-positions but substituted in the p-position, for example alkylated, in order to introduce the two -CH2-NR 6 R 6 to direct groups to an o-position.
• a solid-liquid phase transfer reaction is carried out in each case in the etherification step 2) using a solid base and in the presence of a phase transfer catalyst in order to increase the conversions.
• the base is added in solid form to the respective Betti base of the formula (IV) or (V) and the reactants are reacted with one another either in an organic solvent or else without a solvent, in particular at room temperature.
• Particular preference is given to using the chloride or bromide, in particular the bromide, and an anhydrous solvent as the leaving group X, in order to suppress the formation of by-products.
• other solvents such as e.g. acetonitrile
• anhydrous 2-methyltetrahydrofuran in particular has proven itself, since it was able to promote the conversions and the selectivities for the desired product the most.
• a sulfonate, such as mesylate or tosylate can also be used as the leaving group, although the use of long-chain fatty alcohol sulfonates would be uneconomical since these are themselves surfactants.
• Tetra-n-butylammonium bromide is a particularly preferred phase transfer catalyst used in accordance with the present invention, although other common catalysts such as a variety of other quaternary ammonium compounds can also be used.
• step 3) is also carried out in a gentle, environmentally friendly manner and with conversion that is as quantitative as possible, since the purification of amphiphilic molecules is usually quite complex.
• an aqueous solution of H2O2 is used as the oxidizing agent, where appropriate Methyl formate is added as an additional solvent, the ether of formula (VI) or (VII) being more preferably reacted with 2.5 to 3 equivalents of H2O2 to ensure complete conversion.
• organic solvents such as dichloromethane or acetonitrile, sometimes with the use of catalysts, are also suitable, an (e.g. 30%) aqueous solution of H2O2 has proven to be the best oxidizing agent.
• organic solvents such as dichloromethane or acetonitrile, sometimes with the use of catalysts, are also suitable, an (e.g. 30%) aqueous solution of H2O2 has proven to be the best oxidizing agent.
• small amounts of organic solvent can be added, for which purpose methyl formate is preferred according to the invention.
• the present invention also provides the amine N-oxide compounds of formula (I) or (II) prepared by the process according to the first aspect: wherein R 1 to R 6 are as previously defined.
• Such amine N-oxide monomers of the formula (I) or corresponding dimers of the formula (II) can not only be prepared from readily available lignin degradation products in a relatively simple and environmentally friendly manner, but are also extremely suitable as surfactants. Due to the high hydrophilicity of the N-oxide group(s) and the hydrophobicity of the aromatic(s), even a single-digit number of carbon atoms in the radicals R 1 to R 5 is sufficient to give the compounds the required amphiphilic character. However, the number of carbon atoms in the radicals R 1 to R 5 is preferably at least 9 carbon atoms.
• non-aromatic rings eg dioxolane
• the present invention also includes dimers of the formula (II) in addition to the amine N-oxide monomers of the formula (I) is due to the synthesis beginning with an aminoalkylation reaction according to Betti/Mannich and using secondary mono- and diamines takes place in an analogous manner, which has been explained in more detail in relation to the first aspect of the invention and is evidenced by the later examples.
• the lower and upper limit for the number of carbon atoms in the radicals R 1 to R 5 relates to the preferred use of fatty alkyl radicals for the etherification of free phenolic OH groups in the starting materials, for their chain length in the literature between 4 to 6 as the lower limit and between 22 and 26 as the upper limit. According to the invention, preference is given to a maximum length of 18 carbon atoms for the fatty alkyl radicals introduced by etherification in the synthesis process or of 4 carbon atoms for the alkyl or alkoxy radicals already bonded to the aromatics in the starting material or, if appropriate, also Alkylthio radicals, which applies in particular to the radical R 4 in the para-position to the ether group R 1 -0-.
• nitrogen atoms in the radicals R 1 to R 5 would also be oxidized to N-oxides with a high probability in the final oxidation step, which would reduce the hydrophobicity of this section of the compounds according to the invention, especially if the nitrogen atoms were not positioned very close to the aromatic ring.
• heteroatoms other than oxygen and sulfur need not be considered.
• one or more of the radicals R 2 , R 3 and R 5 can also represent an amine-N-oxide group -CH2-N + (O')R 6 R 6 , on the other hand, relates specifically to the synthesis process, in the first step of which the aromatic ring can also be aminoalkylated at more than one position - and was, as the examples show.
• R 1 is C6-C22 alkyl, more preferably Cs-C alkyl.
• R 2 is from Ci-C22-alkyl, Ci-C22-alkoxy and -CH2-N + (O')R 6 R 6 , more preferably from Ci-C -alkoxy and - CH2-N + (O) R6 R6 , selected.
• R 3 and R 5 are selected from hydrogen and -CH 2 -N + (O')R 6 R 6 , with more preferably one of R 3 and R 5 being hydrogen and the other -CH2-N + (O') R6 R6 .
• the option -CH2-N + (O′)R 6 R 6 for R 2 , R 3 or R 5 relates to a multiple aminoalkylation of the aromatic.
• R 4 is selected from hydrogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy and more preferably from hydrogen and C 1 -C 4 alkyl and is even more preferably C 1 -C 4 alkyl.
• R 1 is Cs-Ci8-alkyl
• R 2 is Ci-C -alkoxy
• R 3 and R 5 are each hydrogen
• R 4 is Ci-C4-alkyl, especially ethyl or propyl.
• R 2 is particularly preferably Ci-Cw-alkoxy, otherwise, for example when using a derivative of guaiacol or syringol, R 2 is in particular methoxy . In the latter case, when syringol is used, R 5 is also methoxy at the same time.
• R 1 is Cs-Ci8-alkyl
• R 2 is -CH 2 -N + (O')R 6 R 6 ;
• R 3 and R 5 are each hydrogen
• R 4 is Ci-C4-alkyl, especially ethyl or propyl.
• radicals R 6 which can generally comprise up to six carbon and optionally heteroatoms (O, S or especially N), it applies in some preferred embodiments of the second aspect of the present invention that they are each independently selected from methyl, ethyl and dimethylaminoethyl are selected.
• two radicals R 6 bonded to the same nitrogen atom are connected to one another and together with the nitrogen atom form one of the following groups: the asterisk in each case indicating the connection to the aromatic ring.
• each R 6 is methyl and one or both methyl groups of a moiety -N + (O')(CH3)2 is/are linked to one or both methyl groups of such moiety of another molecule of formula (I) connected so that these form a bridge with the
• amine N-oxide compound according to the second aspect of the present invention is selected from the following compounds:
• N,N-dimethyl-1 -(5-ethyl-3-methoxy-2-octyloxyphenyl)methanamine N-oxide (1 ) N,N-dimethyl-1 -(2-decyloxy-5-ethyl-3-methoxyphenyl)methanamine N-oxide (2) N,N-dimethyl-1 -(2-dodecyloxy-5-ethyl-3-methoxyphenyl)methanamine N-oxide (3)
• the present invention relates to the use of the new amine N-oxide compounds of formula (I) or (II) in which the total number of carbon atoms of the radicals R 1 to R 5 should be at least 9 as surfactants .
• FIG. 1 shows a cryo-electron micrograph of an aqueous solution of the amine N-oxide compound (13) from example 13 together with a schematic representation of the micelles to be observed therein.
• Step 1
• 2-dimethylaminomethyl-4-ethyl-6-methoxyphenol (1.05 g, 5 mmol) was added together with 1-bromooctane (0.95 g, 4.9 mmol) and tetrabutylammonium bromide (TBAB) (0.16 g, 0. 5 mmol) as catalyst in 10 ml 2-methyltetrahydrofuran (2-MeTHF) as solvent at room temperature stirred vigorously until a homogeneous solution was obtained, after which solid powdered KOH (0.56 g, 10 mmol) was added and at room temperature for 8 h was stirred.
• 1-bromooctane (0.95 g, 4.9 mmol
• TBAB tetrabutylammonium bromide
• 2-dimethylaminomethyl-4-ethyl-6-methoxyphenol (1.05 g, 5 mmol) was combined with 1-bromooctane (1.06 g, 5.5 mmol) and tetrabutylammonium bromide (TBAB) (0.16 g, 0. 5 mmol) in 10 mL of 2-MeTHF was stirred vigorously at room temperature until a homogeneous solution was obtained, after which solid powdered KOH (0.56 g, 10 mmol) was added and stirred at room temperature for 8 h. Then 25 ml Et2O and 5 ml H2O were added and the aqueous phase was extracted 3x with 10 ml Et2O.
• TBAB tetrabutylammonium bromide
• N,N-dimethyl-1-(5-ethyl-3-methoxy-2-octyloxyphenyl)methanamine (0.96 g, 3 mmol) was initially taken and 3 equivalents of a 30 wt% aqueous solution of H2O2 ( 9 mmol) was added all at once.
• the cloudy reaction mixture was stirred at room temperature overnight or until it appeared clear and homogeneous, indicating complete consumption of starting material.
• a catalytic amount of activated charcoal or MnO2 was then added and the mixture stirred for 24 h, or oven-dried Na2CO3 (1.06 g, 10 mmol) in 5 mL ethanol was added and the mixture stirred for 30 min to remove the excess H2O2 decompose.
• Step 1
• Step 1
• Step 1
• Step 1
• Step 1
• Step 1
• Step 1
• Step 1
• reaction mixture was then extracted 5x with 10 ml Et2 ⁇ D, and the combined organic phases were washed 5x with 5 ml water and then concentrated in vacuo on a rotary evaporator, after which the residue was completely dried in a vacuum desiccator, giving a mixture of the doubly aminomethylated intermediates, 3,4- and 3,6-bis(dimethylaminomethyl)-5-ethylpyrocatechol as a cream-colored powder (yield: 1.20 g; 65.5% of theory).
• Example 1 The reaction took place analogously to that in Example 1, variant 2.2, except that 1-bromododecane was used instead of 1-bromooctane, the KOH was added in two portions (0.28 g each at the beginning and after 2 h) and at the flash chromatography, elution with a petroleum ether/ethyl acetate gradient took place, with 1,1'-(2-dodecyloxy-5-ethyl-1,3-phenylene)-bis(N,N-dimethylmethanamine) as a yellow oil was obtained (yield: 1.53 g; 75.7% of theory).
• Step 1
• the precipitated solid was then filtered off (glass frit, porosity 4), suspended in 10 ml petroleum ether and mixed by means of ultrasound, then centrifuged off and completely dried in a vacuum desiccator, the dimeric intermediate schen product, 6,6'-(piperazine-1,4-dimethylene)-bis(4-ethyl-2-methoxyphenol), was obtained in the form of white needles (yield: 3.40 g; 82.1% of theory .).
• Step 1
• Stage 3 The reaction took place analogously to that in Example 1, but only extremely low conversion was observed because of the poor water solubility of 1,4-bis(2-dodecyloxy-5-ethyl-3-methoxybenzyl)piperazine.
• the optimization of this oxidation reaction with methyl formate as an additional solvent is currently the subject of research by the inventors.
• Step 1
• the parameter for the surfactant properties of the new amine-N-oxide compounds was the critical micelle concentration (CMC), ie the concentration above which micelles can form, the protonated or cationic form of the surfactants using a K100C Force Tensiometer from Krüss Scientific according to the Wilhelmy plate method at 25 °C and pH 3.
• CMC critical micelle concentration
• V1 dodecyldimethylamine N-oxide
• Example 1 the examples according to the invention, with the exception of Example 1, have lower--in fact mostly significantly lower--CMC values than the comparison substance C1 used in a large number of commercially available products.
• the highest CMC value of 4.1 mol/l for the amine N-oxide (1) from example 1, which contains the lowest number of carbon atoms in the radicals R 1 to R 5 also proves its suitability as a surfactant , especially since this value is almost identical to that of the commercially available compound V1.
• cryoelectron microscopy when analyzing solutions of these amine N-oxide surfactants in double-distilled water at concentrations of 10 mg/ml each, a previously unknown phenomenon was surprisingly observed using cryoelectron microscopy: the ends of the worm-like micelles formed by the surfactants are folded in, ie they are not in the extended form as has been consistently reported so far.
• a cryo-electron micrograph of such a solution of the amine N-oxide compound (13) from Example 13 is shown in Fig. 1 together with a schematic representation of the worm-like micelles observed therein, which have a size of 40 nm to 76 nm exhibit.
• the present invention thus provides a process for preparing new amine N-oxide compounds which comprises only three relatively simple synthesis steps and by means of which the new amine N-oxides can be obtained in very good yields and in an economical and environmentally friendly manner are, the great majority of which are suitable for use as surfactants.

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