PROCEDURE FOR THE PRODUCTION OF NEW SACCHAROSE AZIDE OF DERIVATIVES

The invention concerns a procedure for the production of new saccharose azide derivatives, which itself for example for the education of photo-interlacable polymere ones own. Polymere ones, which kovalent due to bound photoactive groups rapidly by light interlaced and so that become insoluble, play an important role, so e.g. with the production of printed circuits or print plates as well as the unorthodox imaging, in the technology in addition, completely generally during the surface refinement by coating processes or for special gluing problems. After already H. Stobbe et al. (Ber. Dtsch. chem. total one 52 B, 666 as well as 55 B, 2225 had begun) with the classical studies of the photochemistry of the Zimtsäure, placed the publications of Minsk et al. (L.M. Minsk, J.G. Smith, W.P. VanDensen, J.F. WRIGHT, J. Appl. Polym. Sci. 2, 302 as well as E.M. Robertson, W.P. VanDensen, L.M. Minsk, J. Appl. Polymere Sci. 2, 808) over Poly (vinylcinnamate) a certain high point on this sector. The networking - and thus - of the polymer molecules with kovalent bound Zimtsäure remainders been made via UV light in a highly specific inter+molecular (2+2) - cycloaddition reaction by viergliedrige cyclobutane rings. Merrill and balance spring (US-PS Nr.3, 002.003) reported for the first time on new photo-interlacable polymers with groups of azides, which change with exposing under splitting off from nitrogen into groups of nitrenes. These are extremely reactive and lead for example by inter+molecular insertion in CH connections to the networking. Since practically all technically important polymer types contain enabled CH connections for the insertion of nitrenes, this networking principle is in principle broadly applicable. A condition is however that those contain polymer molecules suitable functional groups which can be interlaced, over which a kovalente introduction of groups of azides is possible. Hiefür were used so far above all polymers with hydroxyl groups, then e.g. with 3-Azidophthalsäureanhydrid (US-PS Nr.8, 002,00S) or also Azidoarylisocyanaten (H. Holtschmidt and G. Oertel, Angew. Macro mol. Chem. 9, 1 was converted) to polymere azides, in those the groups of azides over Esterbzw. Urethane bridges were bound to the polymer molecules. Such photo-interlacable systems work actually satisfyingly, are however concerning the chemical structure of the polymer molecules - e.g. for the adhesion, stability against etching agents, scratching firmness or thermal stability of the photo-interlaced layers responsible actual partially only under considerable expenditure variable, because one manufactures first the type of polymer with hydroxyl groups, wished in each case, and would bring in a following Folgereaktion the necessary groups of azides in must. The subject of the invention is a procedure for the production more again, opposite UV light of photoactive azide derivatives of the saccharose of the general formula HOOC \ __/N3 o s< oi -, ©j) o O (I), where S for the saccharose remainder, R for hydrogen or linear and/or branched aliphatic carbonic acid remainders of c1 - C18 or the benzoic acid remainder and m for average values of the whole numbers from 1 to 7, whereby m > 2 is. It was found that coatings from mixtures of CH-hältigen polymers and to 40 Gew. - % saccharose azides of the general formula (I) by UV light is photo interlacable, whereby well-known Photosensibilisatoren is added if necessary. The new saccharose azide derivatives (I) with on the average more than two groups of azides per molecule it can be received in accordance with the invention by the fact that one saccharose and/or saccharose ester of the general formula (RO) 8 m - S (OH), (IL), where R, S and m to have, with 3-Azidophthalsäureanhydrid in the desired molar ratio convert the above meaning. Hiebei always develop mixtures of saccharose derivatives with different substitution degrees, so that hiefür only average values can be indicated. In place of saccharose as carriers of the photoactive groups of azides naturally also arbitrary other Monound Disaccharide, in addition, reduced strengths and their derivatives can be used. The conversion of saccharose and 3-Azidophthalsäureanhydrid in the molar ratio 1:3 runs almost quantitatively (see hiezu example 1). The reaction product, in which enzymatically only under 5% not converted saccharose are provable, exhibits an average substitution degree (DSG) of 2,4-Azidgruppen per saccharose molecule according to quantitative IR-spectroscopic analysis. This content of group of azides rises with a molar ratio of the two reaction partners of 1:6 and/or 1:8 to 4,5 and/or 6,5, as is occupied in the following examples 2 and 3. Depending upon the average content of group of azides these new saccharose Asid derivatives contain naturally the corresponding quantity of hydroxyl groups, which lend a more or less hydrophilic character to them, still by Carboxylbzw. Groups of carboxylates one strengthens. This expresses itself e.g. that saccharose azide derivatives with an average substitution degree to approximately 5 [formula (I), R = H] itself still in aqueous alcohol and/or. aqueous Bicarbonatlösung e.g. read, not against it in typically nonpolar organic solvents, like benzene. Verestert one in the saccharose molecule first a part of the hydroxyl groups by aliphatic or also aromatic carbonic acids [see formula (II)] and introduces only according to invention thereafter the groups of azides, then one receives azide derivatives of the formula (I), which are soluble for example in Dioxan or toluol starting from an average entire - substitution degree (entire DSG) at Esterund groups of azides of approximately 5 hydrophobe saccharose -. Naturally the DSG necessary for the solubility in typically organic solvents depends not only on the number, but also on the length of the aliphatic carbonic acid substituents. Thus one receives in each case Saccharoselaurate [formula (I), R = CH - (CH2) 12 - CO] to Lauroylchlorid and/or Benzoylchlorid during the conversion from saccharose with in the molar ratio 1:2 and/or. Saccharosebenzoate [formula (I), R = C5 H5 - CO] with a DSG of approximately 2,3. The conversion of such a Saceharose Laurat derivative with 3-Azidophthalsäureanhydrid in the molar ratio 1:3 still leads to products with a DSG, soluble in Bicarbonatlösung, at groups of azides of approximately 2, which corresponds to a entire DSG of approximately 4.3. If one increases the molar ratio to 1:6, then soluble products with a DSG at azide of 3,7 result in Dioxan and toluol, from which a entire DSG of approximately 6 results. If one begins in place of the Saccharoselaurate saccharose acetates with a DSG of approximately 4, then results product, which is soluble only starting from an additional DSG at groups of azides of approximately 3 in Dioxan. Similar results concerning DSG and solubility will receive with conversions of the Saccharosebenzoats described above (DSG 2.3) with 3-Azidophthalsäureanhydrid in different molar ratios. The sequence of the substitution reactions lets itself turn around in principle also, which is called one can first also the groups of azides and afterwards only the aliphatic or aromatic carbonic acid remainders would bring in. However one must here already work after introduction of the photoactive groups of azides under light exclusion. The conversions of the saccharose and/or the saccharose esters of of the general formula (II) with 3-Azidophthalsäureanhydrid preferentially in polar solvents, like e.g. Pyridin, Dirnethylsulfoxyd (DMSO), Dimethylacetamid (DMA (direct memory access)), dimethylformamide (DMF) or N-Methylpyrrolidon (NMP), at temperatures between 20 and 70°C are accomplished. Those according to invention as output products applicable saccharose ester of the general formula (II) in actually well-known way from saccharose and according to reactive acid derivatives, like Säureanhydriden, Säurechloriden or acid esters, in the polar organic solvents specified above are e.g. manufactured. The längerkettigen fatty acid derivatives of the formula (II) can be manufactured in likewise well-known way also without solvents, since the reaction mixtures of the saccharose with reactive fatty acid derivatives, fatty acid chloride, at temperatures from approximately 30 to 70°C in melted form to e.g. be present. For these conversions all aliphatic linear or branched carbonic acid derivatives with i to 18 carbon atoms, like acetic anhydrid, are e.g. suitable butter acid methyl ester, Laurinoder stearic acid chloride, Pivalinsäurechlorid, 2-Äthylhexansäuremethylester, ISO palmitic acid methyl ester beside Benzoylchlorid or benzoic acid esters. Comparable substituents can be bound to saccharose molecules at place over ester connections in actually well-known way also over Ätheroder urethane connections if necessary. In principle with all differently highly substituted saccharose azide derivatives of the general formula (I), whose middle substitution degree can be determined for example by quantitative regulation of group of IR azides, develop for these ester reactions. These mixtures can, without isolating into discrete uniform individual components, for which by UV light induced networking reactions are used by groups of CH of containing polymer types. In the following examples the production of the new saccharose azide derivatives is more near illustrated. Example 1: (Molar ratio saccharose to 3-Azidophthalsäureanhydrid = 1: 3) g saccharose (0.058 mol) as well as 33.2 g (0.175 mol) 3-Azidophthalsäureanhydrid are solved in 250 ml dry Pyridin and heated up under agitating 5 h on 60°C. After the cooling on ambient temperature and removed in the vacuum the solvent distillative is filtered. Yield: 48.2 g (98% d.Th.); average substitution degree at azide remainders (DSG) = 2.4 example 2: (Molar ratio saccharose to 3-Azidophthalsäureanhydrid = 1: 6) the execution of this reaction takes place similar to example 1: g saccharose (0.058 mol) 65.8 g 3-Azidophthalsäureanhydrid (0.35 mol) 250 ml dry Pyridin yield: 81.5 g (95% d.Th.); DSG = 4.5 example 3: (Molar ratio Saecharose to 3-Azidophthalsäureanhydrid = 1: 8) the execution of this reaction takes place similar to example 1: g saccharose (0.058 mol) 88.4 g 3-Azidophthalsäureanhydrid (0.46 mol) 250 ml dry Pyridin yield: 103.0 g (95% d.Th.); DSG = 6.5 example 4: (Molar ratio saccharose to Lauroylchlorid = 1:2; Molar ratio Saccharoselaurat to 3-Azidophthalsäureanhydrid = 1: 6) g saccharose (0.058 mol) will become solved in 225 ml dry Pyridin and under ice cooling 25.6 g Lauroylchlorid (0.12 mol) so course-dripped that the temperature does not rise over 18°C. Afterwards 1 h with 70°C and 24 h are agitated at ambient temperature. After the evaporation of the solvent the reaction mixture is extracted taken up to water, with ether, dried over sodium sulfate and removed the solvent by more-constant evacuating. Yield: 28.5 g (68.8% d.Th.) g Saccharoselaurat (0.025 mol) as well as 32 g 3-Azidophthalsäureanhydrid (0.16 mol) are heated up in 250 ml dry Pyridin under agitating 5 h on 60°C. After the Abdestillieren of the Pyridins in the vacuum with water one washes and one extracts with ether. Yield at extraction arrears: 34.75 g (66.8 d.Th.); DSG = 4,6; average substitution degree at Carbcnsäureresten = 2.4 example 5: (Molar ratio saccharose to carbonic acid derivative = 1:2; Molar ratio saccharose ester to 3-Azidophthalsäureanhydrid = 1: 6) execution takes place similar to example 4: g saccharose (0.058 mol) 225 ml dry Pyridin g stearic acid chloride (0.12 mol) yield: 33.1 g (65% d.Th.) Saccharosestearat g Saccharosestearat (0.023 mol) 26 g 3-Azidophthalsäureanhydrid (0.14 mol) 250 ml dry Pyridin yield: 25.7 g (86% d.Th.); DSG = 4,4; average substitution degree at C arbonsäureresten = 2.3 example 6: (Molar ratio saccharose to carbonic acid derivative = 1:2; Molar ratio saccharose ester to 3-Azidophthalsäureanhydrid = 1: 5) g saccharose (0.058 mol) will become solved in 225 ml dry Pyridin and under ice cooling 16.4 g Benzoylchlorid (0.12 mol) so course-dripped that the temperature does not rise over 18°C. Afterwards 1 h with 70°C and 24 h are agitated at ambient temperature. After the evaporation of the solvent the reaction mixture is extrabiert taken up to water, with benzene, dried over sodium sulfate and removed the solvent by evacuating lasting several hours. Yield: 20.1 g (62.5% d.Th.) g Saccharosebenzoat (0.031 mol) as well as 28.7 g 3-Azidophthalsäureanhydrid (0.15 mol) are heated up in 250 ml dry Pyridin under agitating 5 h on 60°C. After the cooling the solvent in the vacuum is abdestilliert. Yield: 35.1 g (64.8% d.Th.); Entire DSG = 4,4; average substitution degree at carbonic acid remainders = 2.0 example 7: (Molar ratio Saecharoseazidester to carbonic acid derivative = 1: 3) g saccharose azide ester (DSG = 4.5) (0.024 mol) as well as 7.4 g acetic anhydrid (0.072 mol) in 250 ml dry Pyridin 5 h under agitating on 60°C are heated up. After the Abdestillieren of the solvent in the vacuum the reaction mixture is washed with water and dried in the vacuum. Yield: 17.0 g (75.1 d.Th.); Entire DSG = 6,9; average substitution degree at carbonic acid remainders = 2.6 all reactions in the examples 1 to 7 must be led under light exclusion; in place of Pyridin in the same way DMF can; DMSO, DMA (direct memory access) or NMP as solvents to be used.