DE2120301A1 - - Google Patents

Description

Dipl. Phys. Dr. Walther Junfus

Hanover, Abbes *. 20th

April 23, 1971 Dr.J / Κ. My files:

Vyzlcumny frstav organickych syntez Pardubioe-Bybitvi

Aminoindane sulfonic acids and decay for their production

The invention relates to aminoindanesulfonic acids and methods for their production from AminojJdan.

The essence of this invention lies in the heating of the Aminoindanaize, which from the Aminoindanen and sulfuric acid, possibly Chlorosulfonic acid.

The literature does not give any information on the technical utilization of the aminoindanesulfonic acids, although they do

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as intermediate paint products, ζ. B. could be used in azo dye production. It might also be possible be to let the amino indane sulfonic acids react further to get new intermediates.

The aminoindanesulfonic acid of the general formula

in which X is hydrogen, alkyl, alkoxyI or halogen, is according to this invention by the action of sulfuric acid or Ghlorsulfosäure on aminoindane general formula

in which X previously has the meaning given. The resulting salts are at 150-280 ° G during Heated for 1 to 40 hours, preferably under reduced pressure, possibly in the presence of solvents. the recovered products are separated. As a starting reaction component, it is possible to use the mixture of Aminoindanes of the general formula

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in which X has the meaning given earlier.

It is possible to demonstrate the manufacturing process using the following scheme:

respectively.

HSO ₃ Cl

Sulphonizing by frying

(in which X is hydrogen, alkyl, alkoxyl or halogen), the sulfo group in the free p- or enters o-position to the amino group. According to the new procedure it is possible to synthesize the sulfonic acid from 4- and 5-aminoindanes and also from the derivatives that make up the amino-

1 098AB / 1 RAO

group in the 4- or 7- position according to the given reaction scheme, possibly from the derivatives with the amino group in the 5- or 6- position.

From the 5-aminoindan is obtained by this process exclusively 5-aminoindan-6-sulfonic acid, which is only one Contains a small amount of unreacted 5-aminondane and small amounts of impurities. The entrance of the sulfo group exclusively in the 6- position is surprising, because according to the theoretical possibilities and also according to the So far experience with the baking process one could expect the formation of the two isomers according to the following scheme:

The new process produces 4-aminoindan-7-sulfonic acid from 4-aminoindane with a low content of impurities

10 9 8 Λ 6/1 840

opportunities. The animal made 5-Aminoinda ^ -6-sulfonic acid and 4-Aminoindane-7-sulfonic acid has not yet been described in the literature either.

The necessary salts are prepared so that z. B. Aminoindan dissolves in a minimal amount of benzene or in other suitable solvents and slowly dissolves the resulting solution in HpSO. added, the ratio between H ₂ SO. and aminoindan usually chosen so that 1 mole of aminoindane 1 mole of H ₂ SO. is equivalent to. During the synthesis it is advisable to use dilute sulfuric acid (60-80 #), the degree of dilution of the sulfuric acid eliminating the possible course of a direct sulfonation of the amine-danes. In the majority of cases it is possible to work without solvents by mixing the liquid aminoindane with suitably diluted sulfuric acid, but the reaction can also be carried out in the presence of solvents. Before the Aminoindansalze is actually baked, either the solvent is distilled from HpSO with diluting water. preferably under reduced pressure, or carries out the entire baking process in the presence of the solvent, preferably with water distilling off. It is possible to work the other way around in such a way that H ₂ SO. or adding chlorosulfonic acid to the aminoindane solution. It is advisable to stir the reaction mixture while the mixture is being mixed. If the mixing is carried out at an elevated temperature, a homogeneous solution can be obtained. Before the actual baking, the reaction mixture can be freed from the water and also from the solvent by heating in a vacuum. It is also possible

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borrowed molten amine instead of the aminoindane solution to use, mixed with dilute sulfuric acid or chlorosulfonic acid, preferably at elevated temperature even if the resulting sulfate remains in the melted state. That is also successful Production of the salt, if the aminoindanes are used in powder form and in batches in the acid, which is possibly heated to 100 - 120 ° C, adds.

The actual sulfonation by baking is carried out by heating the specified salts at higher temperatures by. The solid product is usually formed during the reaction. It is advantageous to conduct the reaction in such a way that that the mixture of the components is either in a thin layer in a reactor without a stirrer (mostly a crust is formed) or in a suitable reactor with a stirrer (vessel with stirrer, Venulet, ball mill reactor etc.) is located. These two conditions facilitate the course of the reactions with the components in solid form. It is possible to work in such a way that the acidic amino indane sulfate or the analogous Salt with the chlorosulfonic acid in the stirred reactor in the Medium of high-boiling solvents (e.g. o-dichlorobenzene, Trichlorobenzene, decalin, chlornaftalen, formamide, sol-ventnaphta, Petrol etc.) is heated. If one uses the latter method, one can use the aminoindar salts prepare just in this medium, z. B. so that the amine solution in dichlorobenzene with the certain amount the sulfuric acid, possibly chlorosulphonic acid, mixed.

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The baking process can be carried out at atmospheric pressure. It is useful, however, to reduce the pressure to use, because then better conditions exist for the water of reaction or hydrogen chloride removal.

If unreacted starting aminoindan is contained in the reaction product, this can be done, for. B. so eliminate, that the reaction mixture after the addition of water alkalized with carbonates or hydroxides of alkaline metals to a weakly alkaline reaction. Aminoindan is distilled off with steam or from the water solution with a suitable organic solvent (Toluene, xylene, etc.) shaken. The resulting aminoindanesulfonic acid is then isolated using mineral acid. The precipitated product is separated mechanically, e.g. B. by filtration or by centrifugation. So it is possible, for. B. 5-Aminoindan-6-sulfoic acid as a salt of alkali metals or alkaline earth metals or in connection with other cations. It is carried out in such a way that the water solutions with the corresponding oxides, hydroxides or salts weak acids have been neutralized, compressed to crystallize or evaporated to dryness. In many In some cases, it is possible to process the water solutions of the aminoindansulfonane, if possible beforehand unreacted aminoindane was eliminated.

The new process makes it possible to convert the sulfonic acids or sulfonanes from 4- and 5-aminoindanes,

1 09846/1840

from their halogen derivatives (z. B. 4-GhIor-5-amino- and 4-bromo-5-aminoindan), from 4-amino-5, 6-dihalogenindanes, from alkyl, alkoxyaminoindanes and similar compounds to win.

Similarly, it is also possible to process mixtures of amino indanes, e.g. the mixture of 4- and 5-amino indanes offers the new process produces a reaction mixture that contains practically only two sulfonic acids, namely 4-aminoindane-7-sulfonic acid and 5-aminoindane-6-sulfonic acid and only small amounts of contamination *. During the separation of both sulfoisomers it is possible to use the differences in their physical properties. E.g. that The reaction mixture is diluted after baking the mixture of acid sulfates of 4- and 5-aminoindanes with water and neutralized with sodium hydroxide solution, the residues of the unreacted indane are removed by steam, then the reaction mixture is compressed and allowed to crystallize freely. The less soluble sodium salt of 5-Aminoin.dan-6-sulfonic acid is excreted · After filtration, after washing through with ethanol and after After drying, the product contains only small amounts of isomeric 4-aminoindane-7-sulfonic acid. By further thickening the mother liquor it is possible to win the rest of the liatrium-5-Am: Lnoindan-6-sulfonan, and through the addition of acid to the remaining filtrates separates the 4-aminoindane-7-sulfonic acid. By refining of the separated isomers (e.g. through crystallization or precipitation) it is possible to obtain pure isomers.

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example 1

In a glass vessel with a flat bottom, mix .144 g of 68% sulfuric acid with 133 g of 4-aminoindane. White crystals of 4-aminoindane sulfate are obtained. The vessel is then placed in an oil bath and heated to 190 ° G at atmospheric pressure (the product melts at 180 °). The reaction mixture is kept at a temperature of 190 ° C. for 10 hours. During this time, the reaction water and the reaction mixture distilled off. becomes solid. 223 g of the product are dissolved in 2 1 H ₂ O and 600 ml 2.5 1 Ka ₂ CO ₅ . Unreacted 4-aminoindane is distilled off from the solution. Concentrated hydrochloric acid is added to the water solution. At a pH value of about 3 to a fixed proportion wins, the filtering off and durchwäscht with 150 ml of water, ^r is acidified with 10 ml concentrated hydrochloric acid. After drying at 140 ° G, 170 g of gray product are obtained. ^:

Chromatography has been shown to isolate Product is uniform and that almost all impurities are included in the piltrates. Also the interpretation of the NME. Analysis shows that it is 4-aminoindane-7-sulfonic acid acts.

By. Sample obtained recrystallization from water was obtained at 110 ° C
structure:

was dried at 110 ° C and has the following elementary

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COPY

Analytical Pur CqH ₁₁

determined ^ ₃ ^ _berecimet;

Hydrocarbon ^ _n , _t ·. ^ _{n n} « ₀ / cn an 0 /

st off salary ^{50 '11 y} °> ^5Ü ' ^{08 / o 50 '69 / o}

Hydrogen- ^ ₃₇ ^. ^ ₅₅ ^. _{5> 20} ^

! econtains ⁸¹ " ^{15 '19} ^ ¹⁵ ' ¹³ ^ ^{15 '03 7} °

Example 2

As in Example 1, 4-aminoindane is mixed with £ 68.03

Before heating in an oil bath one closes the apparatus to a water jet pump and the heating leads up to 190 ⁰ G slowly for 2 hours in vacuo at 25 torr. The 10 hour reaction hold time also proceeds at the reduced pressure of 25 Torr. 213 g of gray solid mass are obtained, which are dissolved and processed further as in Example 1.

175 g of 4-aminoindane-7-sulfonic acid are obtained,

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INSPECTED

Example 3

144 g of 68 ° /> ± ge HpSO are mixed in an apparatus analogous to that in Example 1. and 133 grams of melted 5-aminoindane. Heating in an oil bath at reduced pressure (25 torr) melts the sulfate at a much lower temperature than in the case of the 4-amino isomer. Analogously to Example 1, the contents of the vessel are heated to 190 ° C. for 2 hours and kept at this temperature for 10 hours under a reduced pressure of 25 torr. 213 g of gray compact mass are obtained, which are further processed in the same way as in Example 1.
175 g of product are obtained.

Ghromatographically it was shown that the isolated product is uniform, 'without impurities. From the interpretation of the NMR analysis it appears that it is is 5-aminondan-6-sulfonic acid.

The ge by recrystallization of the product from water

The sample obtained was given the following elementary structure at 110:

Determined analytically

G dried and has fol-

Kir C

_calculated .

Hydrogen ^
old & old

Nitrogen content

Sulfur content

50.43 *; 50.45

"M 5 * 34 £ 6.32; 6.34

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50.69 1 °

$ 5.20>

6.57 io

15.03 ^a / o

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OWGINALINSPECTED

Example 4

144 g of 68% HpSO. mixed with 133 g of one Mixture of amino indanes, the $ 60 4 - amino and $ 40 Contains 5-aminoindane and can react as in Example 1. 206.5 g of solid content are obtained, the 4-aminoindane-6-sulfonic acid and contains only small amounts of contamination. After dissolution, neutralization and distillation of the unreacted amines, the solution is compressed by evaporation to a volume of 1.3 l The solid part (I) separates out free crystallization. After further thickening of the mother liquor by evaporation to a volume of 600 ml and by free crystallization one obtains the fixed part (II).

The effect of concentrated hydrochloric acid on the filtrate separates the last solid fraction (III).

Paper chromatography showed that Portions I and II contain predominantly 5-aminoindane-6-sulfonic acid and only a small amount of the 4,7 isomer. The proportion III presents the crude 4-aminoindan-7-sulfonic acid. The yield of the sodium 5-aminoindane-6-sulfonan is 90 g (the parts I and II) and the yield of 4-aminoindane-7-sulfonic acid is 8.5 g (the part III).

Example 5

133 g of 5-aminoindane are dissolved in 150 ml of o-dichlorobenzene,

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then there is 90 109 g H ₂ SO follow. to. The reaction mixture is heated to the boil while stirring and is kept boiling for 15 hours. During the boiling, the water of reaction is distilled off by means of an approach for separating the water from the azeotrope. After the reaction has ended, the product is shaken in 200 ml
3% NaOH, 20 ml of concentrated hydrochloric acid are added to the water layer, the solid fraction which has separated out is filtered off and washed through with water that has been acidified with HGl.
162 g of 5-aminoindane-6-sulfonic acid are obtained.

Example 6

133 g of 4-aminoindane are mixed with 150 ml of o-dichlorobenzene and, while stirring, 177 g of chlorosulfonic acid are added. The reaction mixture is heated to boiling and
it keeps it boiling for 15 hours as in Example 5. The product is then processed in the same way as in Example 5.
160 g of 4-aminoindane-7-sulfonic acid are obtained.

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Claims (3)

-H- claims: 1./iminoindanesulfonic acids of the general formula I in which X is hydrogen, alkyl, alkoxyI or halogen indicates. 2. Process for the preparation of the aminoindanesulfonic acids according to claim 1, characterized, that one on the aminoindanes of the general formula II in which X is hydrogen, alkyl, alkoxyl or halogen, acts with sulfuric acid or chlorosulphonic acid and the obtained salts to the temperature 150 - 280 ° J heated for 1 to 40 hours, preferably under reduced pressure, possibly in the presence of the solvent and the obtained products of the general formula III 109846/1840 - 15 in which X has the meaning given above, separated. 3. Method according to claim 2, characterized, that one in the .Reaktion the mixture of isomeric aminoindanes of the general formula IV in which X has the meaning given earlier, introduces, 109846/1840