DE4103681C2 - Derivatives of disaccharide alcohols, process for their preparation and their use - Google Patents

Description

The present invention relates to derivatives of disaccha radical alcohols, namely fatty acid esters and alkoxylation products of α-D-glucopyranosyl-1,6-mannitol, hereinafter Called GPM, and of α-D-glucopyranosyl-1,6-sorbitol, im called GPS, and mixtures of these two Disaccharide alcohols. The nearly equimolar mixture This disaccharide is as a sweetener under the name Isomalt (Palatinit®). The The invention further relates to methods of preparation of these new derivatives and their uses.

Mono- and disaccharides, such as glucose or sucrose, who increasingly as renewable raw materials for the Her position of numerous special products. For example, sucrose esters have been used for some years now as valuable mild and biodegradable additives in of cosmetics and used in the food industry.

From sucrose is in a large-scale process over an enzymatic transglucosidation the reducing Disaccharide isomaltulose (Palatinose®) won. The Hydrogenation of isomaltulose in aqueous neutral solution with hydrogen on the nickel catalyst provides the known Sweetener isomalt (Palatinit®) as approximate Equimolar mixture of the two isomers GPM and GPS.

For simplicity, the following will apply to each other Mixture of these two isomers in the range from 5 to 95% by weight GPM or 95 to 5 wt .-% GPS uses the name isomalt. These are the starting material for the new invention Derivatives.

It is known that the selective esterification of sucrose, due to the limited thermal stability and by the Presence of several equally reactive hydroxyl groups, with considerable difficulties. In the past known processes for the preparation of mono- and disaccharide esters is the implementation of methyl esters in the presence of organic basic catalysts in dimethylformamide or Dimethylsulfoxide described as a solvent. A large Disadvantage of these methods is that the toxic Solvent DMF or DMSO after transesterification completely from the Reaction mixture must be removed (see US-PS 3,251,829, U.S. Patent 3,349,081).

In DE-OS 34 30 944, the production of sucrose esters from fatty acids, sugars and catalytic amounts of a described lipolytic enzyme. The disadvantages of this method are that very high amounts of enzyme from 10 to 200 wt .-%, based on sugar, and the reaction products only after 72 hours of reaction time with the purified toxic solvents chloroform and tetrahydrofuran and have to be worked up.

Recently, from DE-AS 24 12 374 also a solvent-free Transesterification has become known. After this Process is the reaction with molten sucrose, fatty acid triglycerides and K₂CO₃ (5 to 10 wt .-%) at 125 to  130 ° C performed. Although isomalt has a similar high molecular weight (344) and a similar number of OH groups (9) like sucrose (molecular weight 342, 8-OH groups), However, this process can hardly be transferred to isomalt, since the products obtained after a short reaction time very become dark and the total yield of mono- and diesters far below 30%. This method provides a complex reaction mixture, which did not react to an increased degree Contains starting materials.

JP-A 60-204710 describes a monoester mixture of Palatinit® (Isomalt) for dental care. It becomes a Palatinit® lauric acid monoester mixture with an average degree of esterification of 1.2 and a monoester content of 80%, in the usual way by esterification with acid chloride was produced.

GB-PS 1 082 673 describes a process for the preparation of polyethers, wherein a polyhydroxy compound with at least 3 hydroxyl groups with an alpha-beta-alkylene oxide in the presence of basic, secondary amines implemented as catalysts becomes. As the polyhydroxy compound, sucrose, Sorbitol or alpha-methyl glucoside.

DE-OS 14 43 026 describes a process for the preparation a polyol polyether by reaction of the aqueous solution a saccharide with propylene oxide in the presence of a hydroxyalkylation catalyst. It is particularly preferred sucrose used.

DE-OS 24 23 278 describes a process for the preparation of carboxylic acid esters of linear aliphatic polyalcohols,  wherein a fatty acid with a polyhydric alcohol or its glycosides in the presence of at least 10% by weight of a fatty acid soap is esterified at temperatures of 100 to 190 ° C. When Glycosides become hydrogenated, reducing oligosaccharides used.

The US-PS 3,102,114 describes polyoxyalkylene derivatives of Sucrose esters with long-chain fatty acids. For the production of these compounds is an alkyl ester of a fatty acid with 8 to 22 carbon atoms by reaction with sucrose a temperature of 80 to 120 ° C under reduced pressure implemented. The solvents used are dimethylformamide, dimethylacetamide or acylmorpholines.

The chemical composition of isomalt esters and the Configuration of these products are currently in the art not described. This information is very much important for determining the areas of application of these compounds. It has been found that pure or nearly pure monoisotopic esters, due to their high HLB values, as excellent Solubilizer for perfumery ingredients, flavorings for drinks, bakery products, jams, ice cream and pharmaceutics can serve. You can also go for the production of clear shampoos, bath preparations and as O / W emulsifiers used in the production of chocolate, puddings, desserts etc. become. In contrast, the diesters or nearly pure diesters of isomalt as excellent mild thickeners and W / O emulsifiers for cosmetic preparations use Find.

The technical problem of the present invention is initially in the provision of configurational characteristics monoesters and diesters of isomalt as well as alkoxy lated and polyesterified derivatives by means of a Process for the solvent-free production of new ones Mono- and diesters and alkoxylation of the Isomalts and their mixtures. The procedure should be in simple manner be feasible and thus special suitable for industrial scale applications, at the same time by the use of toxic solutions medium occurring problems of the prior art ver avoid. Preferably, it is a selective esterification allow for primary OH groups of the isomalt.

The technical problem is inventively characterized ge solves that derivatives of disaccharide alcohols of all common formulas I and II

be provided, wherein X is hydrogen or an acyl radical a saturated or unsaturated fatty acid of 8 to 20 Carbon atoms or the rest

means, where R₃ represents hydrogen or a methyl group, and n im Range 1 to 20, R₁ and R₂ are the same or different and may have the same meaning as X, but not both may be hydrogen at the same time if X is the same Is hydrogen, as well as their isomer mixtures.

The derivatives according to the invention are prepared by α-D-glucopyranosyl-1,6-mannitol or α-D-glucopyranosyl-1,6- sorbitol or isomer mixtures thereof either for the production of the ether in aqueous alkaline solution at elevated Temperature be reacted with ethylene oxide or propylene oxide or for the preparation of the esters without solvent in the presence alkaline catalysts at elevated temperatures with saturated or unsaturated fatty acids having 8 to 20 carbon atoms implemented and, where appropriate, also with Ethylene oxide or propylene oxide are reacted.

In a particular embodiment, the inventive Derivatives or mixtures thereof with 2 to 150 moles of ethylene oxide or propylene oxide alkoxylated.

In a further preferred embodiment, the mono- or diesters of the general formulas I and II (X =H) or their mixtures with fatty acids, fatty acid esters, anhydrides or halides to derivatives containing 3 to 9 ester groups included, implemented.  

Alkaline or alkaline earth oxide, hydroxide, carbonate, peroxide, bicarbonate or alcoholate be used. The inorganic salts can be used as such or in combination with the alcoholates of sodium, Potassium or lithium can be used. Preferably, the Catalyst from 0.01 to 10 wt .-% of these substances.

The preferred fatty acids are capric acid, lauric acid, Myristic acid, palmitic acid, stearic acid, isostearic acid, Coconut fatty acid, ricinoleic acid, oleic acid, linoleic acid and undecylenic acid used. In place of pure fatty acids can also Fatty acid mixtures can be used from natural fats.

The esterification is preferably at temperatures between 90 and 180 ° C at atmospheric pressure or in a vacuum. When Alcohol component, the isomalt is used.

Starting from the prior art, according to which the esterification of the Disaccharides exclusively via the reaction of methyl esters in solvents, it is extremely surprising that in a direct reaction by means of a basic catalyst effective, bright products without decomposition or caramelization and with a significantly higher proportion of the desired mono- and Diester to be obtained.

It is also surprising that in the inventive Process preferred only the primary OH groups esterified be, where new mono- and diesters of isomalt or their isomer mixtures are formed as main reaction products.

Another interesting aspect of the invention is that that both the isomalt as such and the mono- and  Diester of isomalt or their isomer mixtures with ethylene oxide or propylene oxide can be alkoxylated, with new nonionic surfactants and emulsifiers for skin and hair care products to be obtained.

In the prior art, it was common practice for a long time, the transesterifications of fatty acid methyl esters with mono- and disaccharides in Solvents, such as. For example, dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone. Only a few previously described tendencies existed for solvent-free To develop reactions. These led however, as in the beginning shown not to develop a solvent-free Manufacturing process. It is also known that the described Substantially unreacted process Starting compounds, in addition to the solvents must be removed from the reaction product. This effort affected the economy of up to a considerable degree.

In the inventive reaction of fatty acids with isomalt may be the molar ratio of fatty acid to isomalt between 3: 1 to 1: 2 lie. It will be preferred only primary Esterified OH groups, except Monofettsäureestern especially also the difatty acid esters are formed. The content of monofatty acid ester in the final product can be adjusted by adjusting the molar Ratios of fatty acid to isomalt can be varied.

For carrying out the method according to the invention z. B. 1 mole of fatty acid (lauric acid, 200.31 g) with  1 mole of isomalt (average molecular weight of GPS and GPM-Dihy drat; 362.33 g) and the Veresterungskomponen first in a homogenizer, screw reactor or with a high speed stirrer at 70 ° C for one hour intensely stirred. To this homogeneous, lump-free Paste are 0.01 to 10 wt .-%, but preferably 0.1 to 5 wt .-%, of the alkali metal catalyst added. The Reaction temperature is gradually increased to 120 to 140 ° C increases and it will be at reduced pressure for 2 to 6 hours esterified. After the reaction was light brown pasty product analyzed by gas chromatography and the content of mono-, di- and triesters determined. Around the exact chemical structure of the new mono- and diesters of the Isomalt, the above approach was taken from the Equimolar reaction of lauric acid with isomalt such as followed up and analyzed by NMR spectroscopy:

100 g of the ester mixture from the reaction of lauric acid with isomalt were charged with 100 g of methanol and 300 g of water Stirred for 12 hours at 50 ° C. After that, the cloudy reac tion mixture for 24 hours at room temperature gelgelas sen and then filtered off. The residue, one bright soft paste, was dried in vacuo and the Filtrate on a rotary evaporator of the solvents freed. The composition of the two pastes is in listed in the following table:  

Isomalt gives in ² [H] ₅-pyridine or D₂O well resolved and fully interpretable ¹³C-NMR spectra. The isomers GPS and GPM ( FIG. 3) are present in a ratio of 1: 1. The signals of the primary C atoms of the open chain C₁ are at 62.97 and 63.93 ppm. The primary carbon atoms on the pyrano sidring C _{6 '} coincide in the signal at 61.29 ppm.

The esterification carried out by the novel process on the primary hydroxyl groups of the isomalt leads to a significant shift of the NMR signals C₁ and C _{6 '} .

The analytical HPLC separation of the residue showed ne the monoester contains a number of stereoisomeric diesters and Trieste in very small amount. Mono- and diesters of Isomaltes were preparatively separated (mobile phase: Methanol / H₂O = 10: 1).

The molecular weights of the mono- and diesters of isomalt were confirmed by CI mass spectra.  

The following table shows the 13 C assignment of the primary Isomalt C atoms in [ppm] (² [H] ₅-pyridine):

The further table shows the ¹³C assignment of laurin acid chain in [ppm] (D₂O):

Lauri nests signal CH₃ 14.64 C H₂Me 23.39 chain center 30.61

In an analogous manner, the novel esterification products of other fatty acids (C₁₀ to C₂₀) have been worked up in analogy to the lauric acid approach and analyzed. These test results clearly indicate that the mono- and diesters of isomalt according to the invention are not only new, but preferred primary OH groups ( Figures 1 and 2) of the isomalt are esterified in the inventions to the invention process. It is thus isomalt-1-laurinsäuremonoester and isomalt-1,6'-laurinsäurediester. It is also surprising that, in contrast to the known sucrose esters, the inventions to the invention isomaltester have almost no tri- and polyester or cracking products.

The herge in high yields and with a high degree of purity Mono- and diesters of isomalt are compounds gen, the highly effective detergents, emulsifiers and value full additives for numerous cosmetics, pharmaceuticals tika and food. These raw materials will be if desired with 2 to 150 moles of ethylene oxide and / or Propylene oxide alkoxylated to the application technology Possibilities to expand.

Fig. 1 shows the structural formulas of isomalt-1-laurin acid monoester.

Fig. 2 shows the structural formulas of the isomalt-1,6'-lauric diesters.

Figure 3 shows the two structural formulas of isomalt, α-D-glucopyranosyl-1,6-mannitol (GPM) and α-D-glucopyranosyl-1,6-sorbitol (GPS).

The following examples represent particular execution forms of the invention.

Example 1

200.31 g (1 mol) of lauric acid are mixed with 362.33 g (1 mol) Isomalt weighed and with the help of a homogenizer, Screw reactor or a high-speed stirrer at 70 ° C intensively stirred for one hour. The homogeneous, lumps free paste is then in a 2-liter three-necked flask with Stirrer, thermometer and water separator transferred and added with 4.22 g of potassium carbonate. Subsequently, the Reaction mixture heated to 120 to 125 ° C and ver esterified under reduced pressure for 5 hours. The vacuum will be like this adjusted so that no lauric acid from the reac tion mixture is removed.

The amount of water separated was 17.2 g. After finishing The reaction was 536.35 g of a light brown, pasty product. This ester mixture was then used with 536 g of methanol and 1.6 g of water for 12 hours at 50 ° C ge stirred, allowed to stand for 24 hours at room temperature and then filtered off. The residue, a bright white paste, was dried in vacuo and the filtrate on Rotary evaporator freed of solvents, wherein 83.84 g of reaction product enriched with non-reacted were obtained isomalt.

The residue (440 g) contained:

55.19% isomalt monolauric acid ester
33.00% Isomaltdilaurinsäureester
4.00% Isomalttrilaurinsäureester
1.74% lauric acid
0.84% isomalt
3.90% not identif. component
1.33% water.

The product from the filtrate (83.84 g) contained:

4.74% isomalt monolauric acid ester
11.52% lauric acid
82.82% isomalt.

The conversion, based on isomalt, was 79.78%.

Examples 2 to 7

The reaction was carried out as in Example 1. The used fatty acid, the molar ratio, Reaktionstempe temperature and time as well as amount of catalyst and consi The stenz and color of the product are given in Table 1 compiled.

example 8 Presentation of isomalt nonadodecanoate

20 g (55.2 mmol) of isomalt or an appropriate amount of Mono or diester in 200 ml of anhydrous pyridine with stirring within 3 hours dropwise with 131 ml (552 nmol) of lauric acid chloride are added.

After completion of the addition, continue for 1 d at room temperature touched. The precipitated salts are filtered off and washed with washed a little pentane. The combined filtrates become concentrated at about 60 ° C in vacuo. The residue is with Water (200 ml) and pentane (300 ml) are stirred. The pentane phase is washed with 5% hydrochloric acid (200 ml) and again extracted with water (200 ml), with anhydrous sodium dried sulfate and filtered.  

For decolorization, the pentane phase is over a layer Activated carbon / silica gel filtered and then to the Evaporated to dryness.

Yield: 70 g (61% of theory) of a pale yellow ge stained fat-like product with a melting range from 35 to 39 ° C.

Thin-layer chromatography (silica gel 60, eluent: pentane: ether = 5: 1) can be used to separate GPS (R _F = 0.57) and GPM (R _F = 0.61) nonadodecanoate.

The structure of both products could be separated Individual representation of both components by ¹H-NMR-Spek completely protected (300 MHz, CDCl₃) become.

Table 2 shows the composition of isomalt esters Examples 1 to 8.  

Table 1

Table 2

example 9

In a pressure reactor with product cycle, heating, a metered addition of ethylene oxide, pressure and temperature 1000 g of isomalt and 10 g of 45% potash were measured lye added, rinsed thoroughly with nitrogen and subsequently at a reaction temperature of 165 to 170 ° C with 1214 g of ethylene oxide. The reaction was completed after 3 hours, including a post-reaction time of an hour. After cooling to about 30 ° C was neutralized with sulfuric acid. It became one at 20 ° C clear, pale yellow oil with the following characteristics:

hydroxyl number: 630 to 670 mg KOH / g Acid number: 2 Viscosity: 6000 to 6500 mPa · s Water content: 0.05%

example 10

A mixture of 1000 g of isomalt and 10 g of 45% potash lye was as in Example 9 with 2428 g of ethylene oxide implemented. The result is a clear yellow oil at 20 ° C with the following characteristics:

hydroxyl number: 460 to 480 mg KOH / g Acid number: 2 Viscosity: 5000 to 5500 mPa · s Water content: 0.1%

example 11

A mixture of 1000 g of mixed ester according to Example 2 and 10 g of 45% potassium hydroxide solution was as in Example 9 with 1100 g of ethylene oxide reacted at 140 ° C. The resulting white, waxy product had the following characteristics:

Saponification number: | 45 to 55 Acid number: <1 hydroxyl number: 120 to 130 Water content: 0.1%

In the following examples are some typical Applications of new products described.

example 12

Baby shampoo Product according to Example 1 2.0% by weight Product according to example 6 2.0% by weight Sodium lauryl ether sulfate 35.0% by weight cocoamidopropyl 7.0% by weight sodium chloride 2.0% by weight Konservierer 0.1% by weight water 51.9% by weight @ 100.0% by weight

example 13

conditioner Product according to Example 3 2.0% by weight Product according to example 6 2.0% by weight Cetylstearylalkohol 2.5% by weight Cetylstearyl alcohol with 20 moles of EO 0.5% by weight Polyglycol polyamine condensation resin 2.0% by weight glycerin 3.0% by weight Konservierer 0.1% by weight water  87.9% by weight 100.0% by weight

example 14

body lotion Product according to Example 3 2.5% by weight Product according to Example 5 2.5% by weight Cetylstearyl alcohol with 20 moles of EO 2.0% by weight Mono- and diglycerides of palmitic and stearic acid 8.0% by weight Caprylic / capric 4.0% by weight 2-octyldodecanol 8.0% by weight Konservierer 0.2% by weight water  72.8% by weight 100.0% by weight

example 15

moisturizer Product according to Example 3 2.5% by weight Product according to Example 11 2.5% by weight Cetylstearyl alcohol with 20 moles of EO 2.0% by weight Mono- and diglycerides of palmitic and stearic acid 8.0% by weight Caprylic / capric 4.0% by weight 2-octyldodecanol 8.0% by weight Konservierer 0.2% by weight water  72.8% by weight 100.0% by weight

example 16

body lotion Product according to Example 3 3.0% by weight Product according to Example 2 2.0% by weight Cetylstearylalkohol 1.0% by weight Caprylic / capric 5.0% by weight Silicone oil 345 1.0% by weight 1,2-propylene glycol 2.0% by weight citric acid 0.4% by weight Konservierer 0.1% by weight water  85.5% by weight 100.0% by weight

example 17

foam bath Product according to example 6 2.5% by weight Product according to example 7 2.0% by weight Sodium lauryl ether sulfate 35.0% by weight cocoamidopropyl 12.0% by weight sodium chloride 1.5% by weight Konservierer 0.1% by weight water  46.9% by weight 100.0% by weight

example 18

Intimate washing care products Product according to Example 3 5.0% by weight Sodium lauryl ether sulfate 25.0% by weight cocoamidopropyl 15.0% by weight 1,2-propylene glycol 2.0% by weight sodium chloride 0.5% by weight Konservierer 0.1% by weight water  52.4% by weight 100.0% by weight

example 19

Intimate hygiene detergent Product according to Example 3 5.0% by weight Product according to Example 9 3.0% by weight Sodium lauryl ether sulfate 23.5% by weight cocoamidopropyl 13.5% by weight 1,2-propylene glycol 2.0% by weight sodium chloride 0.5% by weight Konservierer 0.1% by weight water  52.4% by weight 100.0% by weight

Claims (8)

1. Derivatives of disaccharide alcohols of the general formulas I and II wherein X is hydrogen or an acyl radical of a saturated or unsaturated fatty acid having 8 to 20 carbon atoms or the radical wherein R₃ is hydrogen or a methyl group, and n is in the range 1 to 20, R₁ and R₂ are the same or different and may have the same meaning as X, but not both may be simultaneously hydrogen when X is hydrogen, and the isomer mixtures. 2. A process for the preparation of derivatives according to claim 1, characterized in that α-D-glucopyranosyl-1,6-mannitol or α-D-glucopyranosyl-1,6-sorbitol or the isomer mixtures thereof

• a) reacted for the preparation of the ether either in aqueous alkaline solution at elevated temperature with ethylene oxide or propylene oxide or
• b) for the preparation of the esters without solvent in the presence of alkaline catalysts at elevated temperatures with saturated or unsaturated fatty acids having 8 to 20 carbon atoms reacted and optionally subsequently also reacted with ethylene oxide or propylene oxide.

3. The method according to claim 2, characterized that with 2 to 150 moles of ethylene oxide or propylene oxide is alkoxylated. 4. Method according to claims 2 and 3, characterized that mono- or diester according to the general Formulas I and II (X = H) or mixtures thereof with fatty acids, fatty acid esters, anhydrides or halides to derivatives, 3 to 9 Ester groups included. 5. Process according to claims 2 to 4, characterized in that that as an alkaline catalyst Alkali or alkaline earth oxide, hydroxide, carbonate, hydrogen carbonate, peroxide or alcoholate used becomes. 6. Process according to claims 2 to 5, characterized that mixtures of different fatty acids be used from natural fats.   7. Process according to claims 2 to 6, characterized marked records that the esterification is preferred at tempera temperatures between 90 ° C and 180 ° C at atmospheric pressure or in Vacuum is performed. 8. Use of the compounds according to claim 1 as Surfactants, emulsifiers, humectants and fat Substitutes in skin and hair care products, pharmaceuticals zeutika and food.