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    • 专利摘要:
    van mono-anhydro—hexitol monoalkylethers met een alkylether groep (OR) C-3, C-5 en C-6 van de mono- anhydro—hexitol, waarbij de alkylgroep (R) een cyclische of niet-cyclische koolwaterstofgroep, lineair of vertakt omvattende 4-18 koolstofatomen. De uitvinding betreft ook de werkwijze voor het verkrijgen van een dergelijke samenstelling en het gebruik ervan als niet ionogene oppervlakteactieve stof, emulgator, J2 smeermiddelen, antimicrobiële middel of p dispergeermiddel. Μ The invention relates to a composition of isomers of mono-anhydro-hexitol monoalkyl ethers with an alkyl ether group (OR) C-3, C-5 and C-6 of the mono-anhydro-hexitol, wherein the alkyl group (R) is a cyclic or non-cyclic hydrocarbon group, linear or branched comprising 4-18 carbon atoms. The invention also relates to the method for obtaining such a composition and its use as a nonionic surfactant, emulsifier, J2 lubricant, antimicrobial agent or dispersant. Μ
    公开号:BE1022369B1
    申请号:E2015/5358
    申请日:2015-06-12
    公开日:2016-03-25
    发明作者:Charlotte Gozlan；Nicolas Duguet；Marc Lemaire；Andreas Redl
    申请人:Université Claude Bernard Lyon I；Syral Belgium Nv；Centre National De La Recherche Scientifique (C.N.R.S.)；
    IPC主号:
    专利说明:

    COMPOSITIONS OF MONO-ALKYL ETHERS OF MONO-ANHYDRO HEXITOLS. PREPARATION METHODS AND THEIR USE
    The present invention relates to compositions based on sugars based on mono-alkyl ethers and a method for obtaining such ethers.
    In the scientific and technical literature, the surface-active molecules based on sugar are well known. Among them, sucrose fatty acid esters, sorbitan esters and long chain alkyl polyglucosides that are widely used in the food industry, personal care, cosmetic and pharmaceutical applications. Some of these surfactants are also widely used as household or industrial cleaners or lubricants.
    Despite their widespread use and acceptance, it is known that the ester-based surfactants are only stable over a limited pH range, while the alkyl glucosides are stable under basic and neutral conditions, but not in a strongly acidic environment.
    Other disadvantages are related to the processes for obtaining these derivatives. After all, in the case of long-chain alkyl glucosides, a trans-glycosylation is necessary. The use of relatively complicated and expensive equipment is necessary to obtain a sufficiently pure product. For sugar-based esters, in particular sorbitan esters, there is a need for expensive and toxic solvents or high reaction temperatures in order to obtain the products in a sufficiently high yield.
    In order to improve the stability in terms of sugar-based acidic surfactants, a sugar alcohol ether was recently proposed in WO 2012/148530. This application describes a process for preparing ethers of polyols in which a mass of molten polyol reacts with a long chain alkyl aldehyde under reductive alkylation and acid catalysis conditions. According to this description, difficult and extreme reaction conditions are required in combination with a high pressure equipment to perform the reductive alkylation reaction. In order to obtain the desired products, an excess of sugar alcohol is considered necessary relative to the aldehyde. This leads to an increased energy consumption per mole of sugar alcohol ether. In addition, at the end of each synthesis, the authors identified by RMN13C the unique synthesized composition (one regioisomer with an alkyl chain at position 6), for example 2- (2-heptyloxy-1-hydroxyethyl) tetrahydrofuran-3,4- diol (example 1), 2- (2-hexyloxy-1-hydroxyethyl) tetrahydrofuran-3,4-diol (example 2) and 2- (2-octyloxy-1-hydroxyethyl) tetrahydrofuran-3,4-diol (example 3 ).
    In addition, the prior art describes methods for obtaining mono-anhydro-sorbitol. Thus, a process in which the sorbitol is dissolved in water in the presence of an acid catalyst and heated under atmospheric conditions for a sufficient time to obtain the maximum 1,4-sorbitan is described in Acta Chemical Scandinavica B (1981) p.441- 449. Similar methods have also been described in which the reaction is carried out under reduced pressure (US 2,390,395 and US 2007/173651) or under moderate hydrogen pressure (US2007 / 173654). In the patent application US2007 / 173654, a noble metal co-catalyst is used. The measured concentrations of isosorbide become quite high compared to 1,4-sorbitan. Therefore, the methods of the prior art are not possible to maintain a high sorbitol mono-anhydro production yield under mild reaction conditions.
    It is therefore clear that there is a need for alcohol ethers of sugars, with surfactant properties, obtained through high efficiency processes that are acceptable to the environment, economical power consumption and easy to implement industrially.
    This need was solved by the introduction of a composition of isomers of mono-anhydro-hexitol monoalkyl ethers with an alkyl ether group (OR) at C-3, C-5 and C-6 of the mono-anhydro-hexitol where the alkyl group (R ) is a linear or branched hydrocarbon group with 4 to 18 carbon atoms, preferably between 8 and 12 carbon atoms. "Alkyl ether group (OR) at C-3, C-5 and C-6" refers to an alkoxy group substituted with a hydroxy group (OH) carried out by a carbon atom on the 3-, 5- or 6 of the mono-anhydro- -hexitol.
    With "isomers monoalkyl ethers of mono-anhydro-hexitol with an alkyl ether group (OR) at C-3, C-5 and C-6 of the mono-anhydro-hexitol" or "isomers at C-3, C-5 or C -6 monoalkylethers of mono-anhydro-hexitol, the mono-anhydro-hexitol-3-alkyl, 5-alkyl-hexitol, mono-anhydro- and 6-alkyl-mono-anhydro-hexitol.
    Examples of alkyl may be mentioned butyl groups, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. Usually the alkyl group is selected from the group of octyl, decyl and dodecyl.
    More in particular, the composition according to the invention comprises at least 1, 2, 5, 10 or 15% by weight of one of the monoalkylethers isomers of mono-anhydro-hexitol. Preferably, the major isomer is 6-alkyl mono-anhydro-hexitol. Typically, isomeric 6-alkyl mono-anhydro-hexitol which is 34-98% by weight of monoalkyl ethers of mono-anhydro-hexitol of the composition of the invention are preferably 40 to 80% by weight, more preferably 45-70% by weight. The mono-anhydro-hexitol-3-alkyl-5-alkyl mono-anhydro-hexitol identical or different proportions and independently represent 1-33% by weight, preferably 5 to 30%, more preferably 10- 27% by weight of monoalkyl ethers of monomers of mono-anhydro-hexitol of the composition.
    The ratio of [(3-alkyl-mono-anhydro-hexitol + 5-alkyl mono-anhydro-hexitol) / 6-alkyl mono-anhydro-hexitol] is between 0.02 and 2, preferably between 0.25. and 1.8 is most preferred, between 0.4 and 1.7, between 0.7 and 1.5 or between 0.8 and 1.2.
    Preferably the composition according to the invention comprises at least 90% by weight, preferably at least 95% by weight of mono-alkyl ethers of mono-anhydro-hexitol isomers.
    The mono-anhydrohexitol is particularly advantageously selected from mono-anhydro sorbitol, mono-anhydro mannitol, iditol and mono-anhydro mono-anhydro galactitol. Typically the mono-anhydrohexitol is mono-anhydro sorbitol or mono-anhydro mannitol.
    Typically, isomers of monoalkylethers of mono-anhydro-sorbitol of formula I wherein R 1, R 2 and R 3 are an alkyl group and two hydrogen atoms.
    For example, an isomer at C-3 of alkyl ether monoanhydroliditol (or 3 alkyl-monoanhydroliditol) the formula II wherein R1 is an alkyl group.
    Preferably, the isomer is C-5 alkyl ether monoanhydrosorbitol (or 5-alkyl monoanhydrosorbitol) of formula III wherein R2 is an alkyl group.
    Preferably, the C 1-6 alkyl ether monoanhydrohydbitol (or 6-alkyl monoanhydrorbitol) isomer is the formula IV wherein R 3 is alkyl.
    The present invention also relates to a process for obtaining a monoalkylethyl monomer alkyl isomer composition with an alkyl ether group (OR) at C-3, C-5 and C-6 of the monoanhydro-hexitol wherein the alkyl group (R) comprises 4 to 18 carbon atoms according to the invention, which method comprises the steps of: - dehydrating a hexitol to obtain a mono-anhydro-hexitol substrate; - obtaining an alkyl acetal hexitan by acetalization or transacetalization of mono-anhydro-hexitol substrate with o a reactive aliphatic aldehyde with 4 to 18 carbon atoms by acetalization, preferably in a substrate / reagent ratio between 5: 1 and 1: 1 or o a derivative of an aliphatic aldehyde reagent comprising 4 to 18 carbon atoms, by trans-acetalization, preferably in a substrate / reagent ratio between 1: 1 and 1: 3 - the catalytic hydrogenolysis of alkyl acetal hexitan and - the recovering a composition of isomers of mono-anhydro-hexitol monoalkyl ethers with an alkyl ether group (OR) at C-3, C-5 and C-6 of the mono-anhydro-hexitol, the alkyl group (R) being 4 to 18 carbon atoms includes.
    Typically, the method according to the invention further comprises at least one neutralization and / or filtration step and / or purification after one of steps a), b) and / or à).
    Step a) of dehydration is preferably effected by treatment with hexitol, for example in the form of a hexitol melt with an acid catalyst. Usually step a) is carried out under a hydrogen atmosphere, preferably carried out at a pressure of 20-50 bar.
    Step a) is particularly advantageously carried out at a temperature between 120 and 170 ° C, preferably between 130 and 140 ° C.
    Step b) acetalization or trans-acetalization can be preceded by a step of purifying the mono-anhydro-hexitol. The purification can for example be a chromatography step or crystallization.
    Preferably, step b) comprises acetalization or transacetalization: bi) optionally a first step of preheating the mono-anhydro-hexitol substrate, preferably at a temperature between 70 and 130 ° C, usually between 90 and 110 ° C. bii) a step of adding reactive aliphatic aldehyde or aliphatic aldehyde derivative and biii) a step of adding a catalyst, preferably an acid catalyst.
    Typically, the acetalization reaction or trans-acetalization is carried out at temperatures between 70 and 130 ° C, usually between 75 and 110 ° C, usually 77-110 ° C. The reaction mixtures were heated to temperatures that vary depending on the reagents and solvents. Typically, an aliphatic aldehyde or aliphatic aldehyde reactive derivative C5 and Cl2, when the solvent is ethanol, temperature acetalization or trans-acetalization can be 80 ° C, when acetalization or trans-acetalization is carried out in the absence of solvent, the reaction temperature can be Be 95 ° C. The reaction time is determined by the conversion achieved.
    Acid catalysts selected independently from solid or liquid acids in steps a) and b), organic or inorganic, solid acids are preferred. Particularly preferred are acids selected from para-toluenesulfonic acid, methanesulfonic acid and camphorsulfonic acid (CSA or camphorsulfonic acid) and sulfone resins.
    During the performance of the acetalization reaction or trans-acetalization with an aliphatic aldehyde or aliphatic aldehyde reactive derivative, the reaction can be carried out with or without a solvent. When the reaction is carried out in the presence of a solvent, the solvent is preferably a polar solvent, typically a non-aqueous polar solvent. When using a solvent, aprotic polar solvents such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMA), acetonitrile (CH3CN), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2 Me-THF), cyclopentylmethyl ether (ether) can be selected. CPME), dibutyl ether (DBE), methyl tert-butyl ether (MTBE) or trimethoxypropane (TMP) or polar protic solvents such as methanol (MeOH), ethanol (EtOH), butanol (BuOH), or isopropanol. Polar protic solvents such as ethanol are particularly advantageous.
    Step b) acetalization can be carried out with a reactive aldehyde, the aliphatic aldehyde reagent comprising 4-18 carbon atoms. These aldehydes can be selected from linear or branched aliphatic aldehydes. In a preferred embodiment, the aliphatic aldehydes comprise from 4 to 18 carbon atoms, preferably from 5 to 12 carbon atoms. Some typical examples of aldehydes are: pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, and dodecanal.
    Extensive experimental work has led to the selection of conditions for an optimal conversion and yield of step b) acetalization. The best results were obtained when the molar ratio of the substrate reagent was between 5: 1 and 1: 1, preferably between 4: 1 and 1: 1, and more preferably between 3: 1 and 2: 1. Step b) trans acetalization can be carried out in the presence or absence of a solvent to obtain long-chain cyclic alkyl-based acetals.
    Typically, if step b) is trans-acetalization in the presence of a solvent, the preferred solvent is the alcohol corresponding to the acetal reagent.
    During step b) trans-acetalization, derivatives of an aliphatic aldehyde reagent may be the di-alkyl acetal of the corresponding aldehydes. Dimethyl acetals and diethyl acetal are preferred.
    Extensive experimental work could ensure the selection conditions in the trans-acetalization reactions, the yield and optimum conversion were obtained when the molar ratio of the substrate reagent was between 1: 1 and 1: 3 and preferably between 2: 3 and 2: 5. The catalysts used are the same as in acetalization reactions.
    Typically in step c) the hydrogenolysis of hexitan alkyl acetal can be preceded by a filtration step and / or purification. The purification can for example be a chromatography step or crystallization. The chromatographic purification is preferably carried out with a non-aqueous polar solvent. For example, the non-aqueous polar solvent is identical to that in step c) hydrogenolysis.
    In an advantageous embodiment, step c) hydrogenolysis is carried out at a temperature between 80 ° C and 140 ° C, preferably at a pressure between 15 and 40 bar. Step c) hydrogenolysis can be carried out with or without a solvent. When performed in the presence of solvents, the solvent may be non-polar, such as, for example, heptane or dodecane. However, polar solvents and especially aprotic non-aqueous solvents are preferred, since equivalent selectivity makes them a better conversion than the non-polar solvents. Examples of aprotic solvents include, without limitation, the trimethoxypropane (TMP), the methyl tert-butyl ether (MTBE), THF, 2 Me-THF, dibutyl ether (DBE) and cyclopentyl methyl ether (CPME). Preferably the aprotic solvent is CPME.
    Step c) Hydrogenolysis is preferably carried out in an aprotic polar solvent at a temperature between 80 ° C and 140 ° C and a pressure between 15 and 40 bar in the presence of a suitable catalyst for the hydrogenolysis reactions.
    Step c) hydrogenolysis is preferably carried out in a non-aqueous polar solvent at a temperature between 100 ° C and 130 ° C and / or at a pressure between 25 and 35 bar.
    Usually, step c) is carried out in the presence of a suitable catalyst such as a catalyst based on noble metals, or based on metals from the ferrous metal group.
    As an indication, a metal-based catalyst of the ferrous metal group nickel, cobalt or iron.
    Hydrogenolysis is preferably carried out using a noble metal catalyst such as palladium, rhodium, ruthenium, platinum or iridium. Usually, the catalyst used in step c) can be mounted on a support such as carbon, alumina or silica. Such a carrier is, for example, in the form of granules. A palladium catalyst on carbon beads (Pd / C) is preferred.
    According to the invention, the hexitol as used in step a) is a hydrogenated monosaccharide, preferably selected from sorbitol, mannitol, iditol, galactitol and mixtures thereof. Sorbitol and / or mannitol are preferred.
    When the hexitol is sorbitol, the monoanhydrohexitol sorbitan obtained is 1.4 sorbitan of formula (V).
    The inventors have shown that the intermediate 1,4-sorbitan can be obtained in good yield by treating a melt of sorbitol with a solid acid catalyst in a hydrogen atmosphere at a pressure of 20-50 bar, this at a reaction temperature which can vary between 120 and 170 ° C, for a period of time sufficient to obtain an optimum performance of sorbitan. Preferred reaction temperatures are between 130 and 140 ° C.
    The reaction mixture thus obtained was extracted from 1,4-sorbitan, sorbitol unreacted isosorbide and small amounts of by-products, as illustrated in the chromatorgram of Figure 1. An advantage is observed as the decrease in the level of staining, in contrast to conventional known methods. Step a) of dewatering can optionally be followed by a purification step of 1.4 sorbitan. Thus 1,4-sorbitan is purified from the reaction mixture and the residue is recycled to the dehydration step. In a specific embodiment, the 1,4-sorbitan is recovered and purified by crystallization. In another preferred embodiment, the 1,4-sorbitan is recovered and purified by chromatography. This purified 1,4-sorbitan is preferably used as a substrate for the acetalization reaction.
    In step b) acetalization without solvent, the 1,4-sorbitan is first heated between 90 and 110 ° C, then the aldehyde reagent is slowly added, followed by addition of the catalyst.
    Acetal sorbitan compositions obtained by the methods described above consist of 4 isomers. This is illustrated in Figure 2. Two of the isomers correspond to a diastereomeric mixture of sorbitan acetal in 5-membered 5,6 position and the other two isomers correspond to a diastereomeric mixture of an acetal sorbitan 6-membered in 3,5 -position.
    Acetal sorbitan in the 5.6 position of the formula VI in which R 'is an alkyl group. Usually R 'is a linear or branched aliphatic chain C3-C17.
    Sorbitan acetals in the 3.5-position have formula VII in which the group R is an alkyl group. Usually R 'is a linear or branched aliphatic chain C3-C17.
    The Alkyl acetals hexitan obtained above are then subjected to a hydrogenolysis reaction. The mixture of acetals can be used after recovery of the crude mixture, and after purification by chromatographic manner. This hydrogenolysis reaction is carried out in an aprotic polar solvent at a temperature between 80 ° C and 140 ° C and a pressure between 15 and 40 bar in the presence of a catalyst suitable for making hydrogenolysis reactions.
    The hydrogenolysis is preferably carried out in a non-aqueous polar solvent at a temperature between 100 ° C and 130 ° C and a pressure between 25 and 35 bar.
    The non-aqueous polar solvent CPME (cyclopentyl methyl ether) was found to be very beneficial in the hydrogenolysis reaction of the cyclic 5.6 and 3.5 sorbitan acetals.
    The invention also relates to the product obtained by applying the method.
    The invention further relates to the use of the composition according to the invention such as ionic surfactant, emulsifier, lubricants, antimicrobial agent or dispersant. Usually the composition according to the invention can be used in a food or non-food or in a pharmaceutical or cosmetic product.
    When the composition of the invention is used as a non-ionic surfactant, emulsifier or dispersion, the food product can be selected from airy products such as mousses, ice cream or non-aerated products such as fat spread or salad dressings. The food product can be in the form of a liquid product selected from the group consisting of sauces, soups and beverages.
    Preferably, the alkyl groups of C10-02 are preferred for use as an antimicrobial or nonionic surfactant.
    Preferably, alkyl groups of C 5 -C 8 are preferred for use as an emulsifier, lubricant or dispersion.
    Without limiting the scope of the invention, the invention will now be further illustrated with the aid of a number of examples describing preparation methods of such derivatives.
    FIGURES
    Figure 1: shows a chromatogram of the reaction mixture obtained in the dehydration reaction according to Example 1;
    Figure 2: shows a chromatogram of the resulting reaction mixture by transacetalization without solvent according to Example 8;
    Figure 3: shows a chromatogram of the resulting reaction mixture by hydrogenolysis according to Example 10.
    Examples Example 1:
    The dehydration of sorbitol: D-sorbitol (20 g, 110 mmol) and 0.1 mol% of camphorsulfonic acid was added to a 150 ml stainless steel autoclave. The reactor is sealed, flushed three times with hydrogen, and then hydrogen is introduced to a pressure of 50 bar. The system is then heated to 140 ° C and stirred with a mechanical stirrer for 15 hours. After cooling to room temperature, the hydrogen pressure was released and the white foam was dissolved in ethanol (200 ml) to obtain a yellow homogeneous mixture. The solvent was evaporated under reduced pressure and the residue was then crystallized from cold methanol and filtered through vacuum. The crystalline material was washed with cold methanol 1,4-sorbitan (5.88 g, 35% of theory) as a white solid: The purity is> 98% as determined by HPLC, while the crystals had a melting point of 113- The reaction degree of the reaction was determined to be 73%, whereby a mixture of sorbitol, 1,4-sorbitan and isosorbide was obtained and some by-products in a very limited amount, whereby the ratio of 1,4-sorbitan: isosorbide was determined. at 80:20.
    Example 2:
    Sorbitan acetalization in DMF:
    In a sealed tube, 1,4-sorbitan (X) (0.5 g, 3 mmol) was dissolved in DMF (1.4 ml). Valeraldehyde (Y) (107 µL, 1 mmol) was added dropwise under argon, followed by addition of camphorsulfonic acid (10 mg, 10 wt%) to close the tube. The mixture is heated at 95 ° C with magnetic stirring. After 15 hours, the dark reaction mixture was cooled and the solvent evaporated under reduced pressure. A conversion of 95% achieved. The residue was diluted in ethyl acetate and excess 1,4-sorbitan was filtered and washed with ethyl acetate. The filtrate was concentrated under reduced pressure. The residue was purified by flash chromatography (EtOAc: cyclohexane 80:20 to 100: 0) to the acetal of sorbitan (0.22 g, 89% isolated yield) as a colorless oil. HPLC showed a mixture of 4 isomers.
    Example 3:
    In this example, different ratios of sorbitan to aldehyde reagent have been tested. The same reaction conditions as in Example 2 were used, but the sorbitan: aldehyde ratio was varied between 1: 1 and 3: 1. The results are shown in Table 1 below.
    Table 1: Effect of sorbitan: aldehyde ratio over the degree of conversion and the isolated yield
    The above results show that the excess sugar is advantageous in that it avoids the formation of by-products such as sugar diacetals. The unreacted sugar can be recovered at the end of the reaction.
    Example 4:
    With a Sorbitan: aldehyde ratio of 3: 1, various reactive aldehydes are used to deliver sorbitan acetal reaction products. The same reaction conditions and the same purification steps as in Example 2 were used. The results are shown in Table 2.
    Table 2:
    Example 5:
    Furthermore, the use of DMF as a solvent, other solvents were also used to prepare the sorbitan acetal compositions. Here too, the same reagents were used and the same procedure was followed as in Example 2 except that the reaction temperatures were at about 80 ° C. The results are shown in Table 3.
    Table 3
    "
    Example 6:
    Acetalization sorbitan without solvent:
    In a sealed tube, 1,4-sorbitan (X) (0.5 g, 3 mmol) was heated to 95 ° C
    Valeraldehyde (Y) (107 µL, 1 mmol) was added dropwise before closing the tube, under argon and camphorsulfonic acid (10 mg, 10 wt%). The mixture is heated at 95 ° C with magnetic stirring. After 15 hours, the dark reaction mixture was cooled and diluted with ethyl acetate (2 ml) and the solvent was then evaporated under reduced pressure. An 80% conversion was obtained. The residue was further diluted in ethyl acetate and excess 1,4-sorbitan was filtered and washed with ethyl acetate. The filtrate was concentrated under reduced pressure. The residue was purified by flash chromatography (EtOAc: cyclohexane 80:20 to 100: 0) until the acetal of sorbitan (0.13 g, 54% isolated yield) was obtained as a colorless oil. HPLC showed a mixture of 4 isomers.
    Example 7:
    Transacetalization of sorbitan in ethanol:
    In a round bottom flask, 1,4-sorbitan (0.5 g, 3 mmol) was dissolved in ethanol (7.5 ml) and 1,1-diethoxypentane (1.15 ml, 6 mmol) was added under a stream of argon and camphorsulfonic acid (50 mg; 10 wt%). The mixture is heated to 80 ° C with magnetic stirring. After 3 hours, the mixture was neutralized and concentrated under reduced pressure. The residue was purified by flash chromatography (ethyl acetate / cyclohexane 80:20 to 100: 0) until the acetal of sorbitan (0.43 g, 66% isolated yield) was obtained as a colorless oil. The HPLC showed a mixture of 4 isomers.
    Example 8:
    Trans-acetalization of the solvent without sorbitan:
    In a round bottom flask, 1,4-sorbitan (0.5 g, 3 mmol) and 1,1-diethoxypentane (1,1-DEP) (1.15 ml, 6 mmol) (mol ratio 1: 2) were added under a stream argon and camphorsulfonic acid (50 mg, 10 wt%). The mixture is heated at 80 ° C with magnetic stirring. After 3 hours, the mixture was immediately purified by flash chromatography (ethyl acetate / cyclohexane 80:20 to 100: 0) to acetal of sorbitan (0.517 g, 73% isolated yield) as a colorless oil. HPLC showed a mixture of 4 isomers. (Fig. 2)
    Example 9:
    Trans-acetalization solvent-free reactions were performed with different molar ratios, different reagents (1,1-dimethoxypentane), different reaction temperatures and different reaction time, the catalyst is the same. Purification of the reaction mixtures was carried out by flash chromatography, as in Example 8.
    The results are shown in Table 4.
    Table 4:
    The reactions of transacetalization of 1,1-DMP or 1,1-DEP are particularly relevant in the solvent-free reaction environment where sorbitan and 1,1-DEP are in stoichiometric ratios.
    Example 10:
    Hydrogenolysis of acetates of sorbitan:
    The pentylidene (1.4) sorbitan (51:49 mixture of regioisomers, 0.98 g, 4.22 mmol) was diluted in dry CPME (30 ml) and placed in a stainless steel autoclave with a 5% catalyst Pd / C (0.45 g). The reactor is sealed three times, flushed with hydrogen before it was under hydrogen pressure (30 bar). The system is heated to 120 ° C and stirred for 15 hours. After cooling to room temperature, the hydrogen pressure is released, the reaction mixture is dissolved in absolute ethanol (100 ml) and filtered (Millipore Durapore 0.01 micron filter). The Alrate is evaporated under reduced pressure and the residue is purified by flash chromatography (EtOAc / cyclohexane 90:10 to 100: 0, then EtOH / EtOAc 10:90). For example, a mixture of ethers pentyl (1.4) sorbitan (0.686 g, 69%) that was obtained as a colorless oil. HPLC analysis (C18 column, eluent water / CH3 CN 80/20 + 0.1% v / v H3 PO4) showed a 27:33:40 mixture of regioisomers of pentyl (1.4) sorbitan at position 5, 3 and 6. The retention times Rt become 7.20 min (27%), 9.25 min (33%) and 10.79 min (40%) (the peaks are assigned to the respective regional isomers at positions 5, 3 and 6) (Fig.3) Spectroscopic data: 1 H NMR (400 MHz, d 6 -DMSO). DELTA.h 0.85 (3H, t, J = 7), 1.20-1.37 (4H, m), 1.38-1.58 (2H, m), 3.20-3.98 (10H, m, + OCH2 proton sorbitan ethers), 4.02-5.15 (3H, 7m, OH protons); 13 C NMR (100 MHz, DMSO-d 6). DELTA.C for major isomer: 13.99 (CH 3), 22.01 (CH 2), 27.88 (CH 2), 28.99 (CH 2), 67 , 50 (CH) 70.59 (CH 2), 73.36 (CH 2), 73.49 (CH 2), 75.66 (CH), 76.37 (CH), 80.34 (CH). .DELTA.C For minor isomers: 14.02 (2 CH 3), 22.03 (2 CH 2), 27.86 and 27.91 (2 CH 2), 29.21 and 29.55 (2 CH 2) , 62.02 (CH 2), 64.20 (CH 2), 68.71 (CH), 69.51 (CH 2), 69.79 (CH 2), 73.15 (CH 2), 73.23 (CH ), 73.60 (CH2), 75.53 (CH), 76.45 (CH), 77.37 (CH), 79.28 (CH), 80.10 (CH), 83.95 (CH) . HRMS (ESI +) calculated for C 11 H 22 Na 5 O: 257.1363 [M + Na] +; Found: 257.1359 (-1.4 ppm).
    Example 11:
    Synthesis "one-pot" of sorbitan ethers of 1,4-sorbitan:
    In a 100 ml round bottom flask, 1,4-sorbitan (10 g, 62 mmol) was dissolved in dry CPME (30 ml) in the presence of Na 2 SO 4 (6.5 g, 50 mmol) under an argon atmosphere. Valeraldehyde (3.3 mL, 31 mmol) was added dropwise, followed by Amberlyst 15 (530 mg, 20 wt% in valeraldehyde). The mixture is heated to 80 ° C with magnetic stirring. After 3 hours the warm mixture is filtered off, washed with CPME (2 x 25 mL) and the filtrate is concentrated under reduced pressure. Without further purification, the mixture was diluted in CPME (300 ml), dried over MgSO 4 and filtered. The filtrate was added in a 500 ml stainless steel autoclave and 5% Pd / C (3.3 mg). The reactor is sealed three times, flushed with hydrogen before the hydrogen pressure is added (30 bar). The system is heated to 120 ° C and stirred for 15 hours. After cooling to room temperature, the hydrogen pressure is released, the reaction mixture is dissolved in absolute ethanol (250 ml) and filtered (Millipore Durapore 0.01 micron filter). The filtrate is evaporated under reduced pressure and the residue (5.8 g) is purified by flash chromatography (EtOAc / cyclohexane 90:10 to 100: 0, then EtOH / EtOAc 10:90). For example, a mixture of ether pentyl (1.4) sorbitan (3.97 g, 56%) obtained as a colorless oil (> 98% purity with RMN 'H).
    Example 12:
    The octyl-1,4-sorbitan is prepared according to the method described in Example 10 from 1,4-octylidene sorbitan (39:61 mixture of regioisomers) (5.61 g, 20.4 mmol). The residue was purified by flash chromatography (EtOAc / cyclohexane 80:20 to 100: 0 then EtOH / EtOAc 10:90) to obtain a mixture of octyl-1,4-sorbitan isomers as a white solid. HPLC analysis (C18 column, eluent water / CH3 CN 80/20 + 0.1% v / v H3 PO4) showed a 33: 22: 45 mixture of regioisomeric octyl (1.4) sorbitan at positions 5, 3 and 6 (the peaks are respectively assigned to the region isomers at positions 5, 3 and 6).
    Spectroscopic data: 1 H NMR (300 MHz, DMSO-d 6). DELTA.h 0.86 (3 H, t, J = 7), 1.08-1.39 (10 H, m), 1.39-1.58 (2 H, m), 3.28-3.95 (10 H, m, + OCH 2 proton sorbitan ethers), 4.02-5.10 (3 H, 7 m, OH protons); 13 C NMR (75 MHz, DMSO-d 6):. DELTA.C for main isomer: 13.98 (CH 3), 22.12 (CH 2), 25.69 (CH 2), 28.73 (CH 2), 28 , 92 (CH 2), 29.31 (CH 2), 31.29 (CH 2), 67.48 (CH), 70.60 (CH 2), 73.35 (CH 2), 73.48 (CH 2), 75 , 64 (CH) 76.36 (CH), 80.33 (CH). DELTA.C juvenile isomers: 13.98 (2 CH 3), 22.12 (2 CH 2), 25.69 (2 CH 2) ), 28.88 (2 CH 2) 28.92 (2 CH 2), 28.98 (CH 2), 29.52 (CH 2), 29.88 (CH 2), 31.32 (CH 2), 62 .00 (CH 2), 64.17 (CH 2) 68.69 (CH), 69.51 (CH 2), 69.82 (CH 2), 73.14 (CH 2), 73.22 (CH) , 73.59 (CH 2), 75.53 (CH), 76 44 (CH), 77.37 (CH), 79.27 (CH), 80.07 (CH), 83.94 (CH) HRMS (ESI +) calculated for C 14 H 28 Na 5 O: 299.1829 [M + Na] +; Found: 299.1832 (-1.2 ppm)
    Example 13:
    Decyl-1,4-sorbitan is prepared according to the method described in Example 10 from decylidene-1,4-sorbitan (36:64 mixture of regioisomers) (6.12 g, 20.2 mmol). The residue was purified by flash chromatography (EtOAc / cyclohexane 70:30 to 100: 0 then EtOH / EtOAc 10:90) to a mixture of isomers of tridecyl 1,4 sorbitan as a white solid. HPLC analysis (C18 column, eluent water / CH3 CN 50/50 + 0.1% v / v H3 PO4) showed a 32: 16: 52 mixture of regioisomeric decyl (1.4) sorbitan at positions 5, 3 and 6 (the peaks are respectively assigned to the region isomers at positions 5, 3 and 6).
    Spectroscopic data: 1 H NMR (300 MHz, d6-DMSO). DELTA.h 0.86 (3H, t, J = 7), 1.09-1.38 (14H, m), 1.38-1.58 (2 H, m), 3.25-4.01 (10 H, m, + OCH 2 proton sorbitan ethers), 4.02-5.08 (3 H, 7 m, OH protons); 13 C NMR (75 MHz, DMSO-d 6). DELTA.C for major isomer: 13.98 (CH 3), 22.16 (CH 2), 25.76 (CH 2), 28.79 (CH 2), 29 , 04 (CH 2) 29.07 (CH 2), 29.14 (CH 2), 29.17 (CH 2), 29.35 (CH 2), 67.53 (CH), 70.63 (CH 2), 73 , 38 (CH 2), 73, 50 (CH 2), 75.69 (CH), 76.40 (CH), 80.35 (CH). DELTA.C Juvenile isomers: 13.98 (2 CH 3), 22.16 (2 CH 2), 28.98 (2 CH 2), 29.01 (2 CH 2), 29.14 (2 CH 2) , 29.17 (2 CH 2), 29.35 (2 CH 2), 29.57 (2 CH 2), 29.92 (2 CH 2), 62.01 (CH 2), 64.18 (CH 2), 68.72 (CH), 69, 56 (CH2), 69.84 (CH 2), 73.16 (CH 2), 73.27 (CH), 73.60 (CH 2), 75.56 (CH ), 76.48 (CH), 77.41 (CH), 79.30 (CH), 80.08 (CH), 83.96 (CH) HRMS (ESI +) calculated for C16 H32 Na05: 327.2142 [M + Na ] +; Found: 327.2135 (+2.1 ppm).
    权利要求:
    Claims (15)
    [1]
    CONCLUSIONS
    Composition of isomers of mono-anhydro-hexitol monoalkyl ethers with an alkyl ether group (OR) at C-3, C-5 or C-6 of the mono-anhydro-hexitol, wherein the alkyl group (R) is a linear or branched hydrocarbon group with 4 to 18 carbon atoms, preferably 8 to 12 carbon atoms.
    [2]
    Composition according to claim 1, characterized in that the mono-anhydrohexitol is selected from mono-anhydro sorbitol, mono-anhydro mannitol, mono-anhydro iditol and mono-anhydro galactitol, and mixtures thereof, preferably the mono-anhydrous sorbitol or the mono-anhydro mannitol.
    [3]
    Composition according to either of Claims 1 and 2, characterized in that it comprises at least 1% by weight of one of the isomers of mono-anhydro-hexitol monoalkyl ethers.
    [4]
    Composition according to any one of claims 1 to 3, characterized in that it comprises at least 90% by weight, preferably 95%, of mono-anhydro-hexitol monoalkyl ethers.
    [5]
    Composition according to any of claims 1 to 4, characterized in that the ratio [(3-alkyl mono-anhydro-hexitol + 5-alkyl mono-anhydro-hexitol) / 6-alkyl mono-anhydro-hexitol] is between 0.02 and 2.
    [6]
    A process for obtaining a isomer composition of mono-anhydro-hexitol monoalkyl ethers with an alkyl ether group (OR) at C-3, C-5 and C-6 of the mono-anhydro-hexitol, wherein the alkyl group (R ) has from 4 to 18 carbon atoms, comprising the following steps: a) dehydrating a hexitol to obtain a mono-anhydro-hexitol substrate; b) obtaining an alkyl acetal hexitane by acetalization or trans-acetalization of the obtained mono-anhydro hexitol substrate, with i. a reactive aliphatic aldehyde with 4 to 18 carbon atoms by acetalization, preferably in a substrate / reagent ratio between 5: 1 and 1: 1, or ii. a derivative of an aliphatic aldehyde reagent comprising 4 to 18 carbon atoms, by trans-acetalization, preferably in a substrate / reagent ratio between 1: 1 and 1: 3; c) catalytic hydrogenolysis of the acetal alkyl hexitane without an acid catalyst, and d) recovering a mixture of isomers of mono-anhydro-hexitol monoalkyl ethers with an alkyl ether group (OR) at C-3, C-5 and C-6 from the mono-anhydro-hexitol wherein the alkyl (R) comprises between 4 and 18 carbon atoms.
    [7]
    Process according to claim 6, characterized in that step b) acetalization or trans-acetalization takes place in the presence of an acid catalyst, preferably in an environment free of solvent or comprising a solvent.
    [8]
    Process according to any of claims 6 and 7, characterized in that the hydrogenolysis is carried out in a solvent or without solvent, preferably at a temperature between 80 and 140 ° C and / or a pressure between 15 and 40 bar, in the presence of a catalyst, preferably a noble metal catalyst.
    [9]
    The method according to any of claims 7 and 8, characterized in that the solvent is a polar solvent, preferably a non-aqueous or aprotic solvent such as cyclopentyl methyl ether (CPME).
    [10]
    Method according to any of claims 6 to 9, characterized in that it comprises at least one filtration and / or purification step after one of steps a), b) and / or d).
    [11]
    Method according to claim 10, characterized in that the purification step takes place by chromatography or crystallization.
    [12]
    A method according to claims 6 to 11, characterized in that the hexitol used is selected from sorbitol and mannitol.
    [13]
    Use of a composition according to any one of claims 1 to 5 as a nonionic surfactant, emulsifier, lubricant, antimicrobial agent or dispersant.
    [14]
    Use of a composition according to any of claims 1 to 5 in a food or non-food, such as a pharmaceutical or cosmetic product.
    [15]
    Product obtained by carrying out the method according to one of claims 6 to 12.
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    FR1401346|2014-06-13|
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