DE4103681A1 - DERIVATIVES OF DISACCHARIDE ALCOHOLS, PROCESS FOR THEIR PREPARATION AND THEIR USE - Google Patents

Abstract

The invention concerns derivatives of disaccharide alcohols of the general formulae (I) and (II), in which X is hydrogen, an acyl group derived from a satured or unsatured fatty acid with 8 to 20 carbon atoms or the group (III) in which R3 is hydrogen or a methyl group and n lies in the range 1 to 20; and R1 and R2, which may be the same or different, may have the same meaning as X, except that they may not both be hydrogen when X is hydrogen. The invention also concerns mixtures of these derivatives, a method of preparing them and their use.

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 of 5 to 95 wt .-% GPM or 95 to 5 wt .-% GPS the name Isomalt used. These are the starting material for the novel derivatives of the invention.

It is known that the selective esterification of saccha rose, due to the limited thermal stability and by the presence of several more reactive ones Hydroxyl groups, verbun with considerable difficulties that is. In the previously known methods for manufacturing ment of mono- and disaccharide esters becomes the reaction of methyl esters in the presence of organic basic Catalysts in dimethylformamide or dimethyl sulfoxide described as a solvent. A big disadvantage of this Method is that the toxic solvents DMF or DMSO after transesterification completely from the reaction tion mixture must be removed (see. US-PS 32 51 829, US-PS 33 49 349 and US-PS 8 90 206).

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

Recently, from DE-AS 24 12 374 also a solution medium-free transesterification known. To In this process, the transesterification with molten Sucrose, fatty acid triglycerides and K₂CO₃ (5 to 10% by weight) at 125 to 130 ° C. Although isomalt  a similar high molecular weight (344) and a sim Liche number of OH groups (9) has like sucrose (Molecular weight 342, 8-OH groups), this can be However, the process is hardly transferred to isomalt, since he kept products very dark after a short reaction time and the overall yield of mono- and diesters far less than 30%. This method provides a complex reaction mixture, the increased not contains reacted starting materials.

JP-A 59-60 439 describes a monoester mixture Palatinit® (Isomalt) for dental care. It will be a Palatinit® lauric acid monoester mixture with one through average degree of esterification of 1.2 and a mono ester content of 80% described in the usual way was prepared by esterification with acid chloride.

The chemical composition of isomalt esters and the Configuration of these products are currently in the state of the art Technology has not been described. This information is but very important for identifying the application areas of these connections. It was found that pure or nearly pure Monoisomaltester, due to their high HLB values, as excellent solubilizers ler for perfumed ingredients, flavorings for drinks, Baked goods, jams, ices and pharmaceuticals can serve. You can also go for the production of clear shampoos, bath preparations and as O / W emulsifiers in the production of chocolate, pudding, desserts etc. are used. In contrast, the di ester or nearly pure diesters of the isomalt as forth outstanding mild thickeners and W / O emulsifiers for kosme tableware find use.

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 with a saturated or unsaturated fatty acid 8 to 20 carbon atoms or the remainder

R₃ is hydrogen or a methyl group represents, and n is in the range 1 to 20, R₁ and R₂ are the same or different and the same meaning can have like X, but not both at the same time What may be hydrogen, if X is hydrogen, as well Mixtures of these derivatives.

The derivatives according to the invention are characterized represents that α-D-glucopyranosyl-1,6-mannitol or α-D- Glucopyranosyl-1,6-sorbitol or a mixture thereof ent neither in aqueous alkaline solution at elevated temperature be reacted with ethylene oxide or propylene oxide or without solvent in the presence of alkaline catalyst 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 inventions Derivatives according to the invention or mixtures thereof with 2 to Alkoxylated 150 moles of ethylene oxide or propylene oxide.

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

As an alkaline catalyst can alkali or Erd alkali, hydroxide, carbonate, peroxide, hydrogen  carbonate or alcoholate. The anorga Niche salts can be used as such or in combination with the alcoholates of sodium, potassium or lithium ver be used. Preferably, the catalyst is made 0.01 to 10 wt .-% of these substances.

The preferred fatty acids are capric acid, lauric acid, Myristic acid, palmitic acid, stearic acid, isostearin acid, coconut fatty acid, ricinoleic acid, oleic acid, linoleic acid and undecylenic acid. Instead of pure fat acids can also be fatty acid mixtures of natural Greases are used.

The esterification is preferably carried out at temperatures between 90 and 180 ° C at atmospheric pressure or in a vacuum guided. The alcohol component is the isomalt used.

Starting from the prior art, after which the esterification the disaccharides exclusively on the implementation of Methyl esters in solvents, it is extremely Surprisingly, that in a direct implementation by means of a basic catalyst effective, bright products without decomposition or caramelization and with considerable obtained higher proportion of the desired mono- and diesters become.

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 mixtures are the main reaction products.  

Another interesting aspect of the invention is in that both the isomalt as such as well as the Mono- and diesters of isomalt or mixtures thereof with Ethylene oxide or propylene oxide can be alkoxylated, new nonionic surfactants and emulsifiers for Skin and hair care products are obtained.

In the prior art, it has long been common for the Um esterifications of fatty acid methyl esters with mono- and Disaccharides in solvents, such as. B. dimethylformamide, Dimethylsulfoxide or N-methylpyrrolidone. Only a few previously described tendencies exist to develop solvent-free reactions. However, these led, as described above, not to Development of a solvent-free manufacturing process proceedings. It is also known that the described Ver drive to a considerable extent unreacted Ausgangsver contain bonds in addition to the solvents must be removed from the reaction product. This Effort impaired the economy of up to a considerable degree.

In the inventive reaction of fatty acids with Isomalt can increase the molar ratio of fatty acid to Isomalt is between 3: 1 to 1: 2. It will be there preferably only primary OH groups esterified, except Monofatty acid esters especially the difatty acid esters arise. The content of monofatty acid ester in the final pro can be adjusted by adjusting the molar ratios of Fatty acid can be varied to isomalt.

For carrying out the method according to the invention be 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 A 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 Drying concentrated.

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 hydrogen at the same time when X is hydrogen, and Mixtures of these derivatives. 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 mixtures thereof

• a) either in aqueous alkaline solution at elevated temperature with ethylene oxide or propylene oxide sets or
• b) without solvents in the presence of alkaline cata- catalysts reacted at elevated temperatures with saturated or unsaturated fatty acids having 8 to 20 carbon atoms and optionally then also reacted with ethylene oxide or propylene oxide.

3. The method according to claim 2, characterized in that with 2 to 150 moles of ethylene oxide or propylene oxide alk is oxyliert. 4. Process according to claims 2 and 3, characterized marked characterized in 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 halo to give derivatives containing 3 to 9 ester groups hold, be implemented. 5. Process according to claims 2 to 4, characterized marked characterized in that an alkaline catalyst is an alkali metal or alkaline earth oxide, hydroxide, carbonate, hydrogen carbonate, peroxide or alcoholate is used. 6. Process according to claims 2 to 5, characterized marked draws that mixtures of different fatty acids natural fats are used.   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.