DE1593359A1 - Process for the preparation of diamido adamantane compounds - Google Patents

Description

Process for the production of diamidoadaaantane * compounds

The invention is baziaht mantanen or adamant Dihydroxycdkyladaraantanen or Dibroa- or _o dichloro-derivatives of Aclamantan anen or alkyl by reaction of these compounds with cyano compounds in the presence of strong or fuming sulfuric acid to 1.3-Diaraidoadamantane as new compounds and their preparation from Dihydroxyada " .,

The carbon core of adamantane (tricyclo </ 3,3,1,1 ³ _'= / = dean) contains 10 Kohlewstoffatome arranged completely symmetrical energized so that to 4 carbon atoms in the bridge position in the rings bef inden _o The structure of Adamantane can be given schematically as follows :

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6AD ORIGINAL

1 5 9 3 3 b

H ₉ C CH ₉

The molecule contains 4 tertiary hydrogen atoms that are calibrated -at the corresponding carbon atoms in the bridge head All 4 bridging carbon atoms are at one end Equivalent and in the same way all rings are equivalent to each other -

The ι prepared by the process of this invention, 3 diamido compounds containing an adamantane group, the a ⁿ lky adamantane consists of a Adama tankers or a modification!, In which one or two alky! Groups on the Adaman depend> tankers, either on a bridgehead Stel-Lung or at a non-bridgehead position. The total number of carbon atoms in the alkyl substituent or in the alkyl substituents is between 1 and 10 including the diamido compounds correspond to the general formula

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BATH ORIGINAL

·· 3

O H - A H O m N N It RC • C

"N where A is the above-mentioned adamantane or alkyladamantane group and R is either a hydrogen atom or is a C, C, g hydrocarbon radical, namely an alkyl, Phenyl, alkaryl or aralkyl group- In these compounds each amido group is on a bridging carbon ■ atom of the adamant core .. So the connections are all 1.3 derivatives of the corresponding adamantane alcohol.

The above-mentioned, inventively producible substance Ir..lasse contains new compounds in which the adamantane nucleus carries carbon atoms on each head of the corner and consequently does not contain any tertiary hydrogen atoms. The substituents at the 1 and 3 positions are the amidocyl groups, and those in the 5 and 7 positions are alkyl groups which contain a total of 2 10 carbon atoms. The alkyl groups can be methyl, ¹ ItHyI, propyl, butyl or the like. act ο The compounds in this subclass are 1,3 Diamido-S ^ -dialkyladaaanta ne, in which the amido group corresponds to:

H "
-NC Ή

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as defined above. Prevented connections in the Sub ™. klaaee are those in which the two alfcyl groups in each case methyl and each diamido group formamides, acetamido or is benzamides,

As mentioned above, these compounds can be used according to the invention from adamantanediols or alkyladamantanediols or from the dibroa or dichloro derivatives of adamantane or alkyladamantanes, in which the hydroxyl groups or halogen atoms are originally on the adamantane core in any bridgehead position or non-bridgehead position or in both positions. These hydroxy compounds or dihalogen compounds are either the ait HCN or with RCN, where R is a C ^ -Cj «-hydrocarbon residue of the ax indicated above, in the presence of strong sulfuric acid implemented. When the resulting reaction mixture is mixed with water, the desired diamido compound is formed by a hydrolysis or solvolysis reactionJ it can be isolated from the mixture The reaction product is the 1,3 diamido derivative of adamantane or alkyl adamantane, even in those cases where one or both of the hydroxy groups in the original diol or one or both of the halogen atoms originally on the nucleus turns into

0 0 9 8 3 1/18 0 3 _ßAn ~

a Nichtbrttckenkopfstellung were, - This result is obtained due to the fact because the strong or fuming sulfuric acid conversion by Isomeri »capitalization effects into a bridgehead of any hydroxyl or Halogenaton that * borrowed in a non-bridgehead position of a carbon atom was origin"

For example, according to one embodiment of the process according to the invention, 1,3-dihydroxy-3, dimethyladamantane with acetonitrile in the presence of fuming sulfuric acid? (KB-, 102% H ₉ SO ,, - equivalents) are reacted and the reaction product is then diluted with water. The reaction is 1,3 <-D! Acetamido -3,5 dimethyl adamantan, which is obtained in white crystals. The reaction to the formation of this product can be represented as follows:

> O <i

+ 2CH ₃ CN

^H 2 ^SO 4

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According to another example of another embodiment of the process according to the invention, 1,3-dibromo-3, 5-dimethyladamantane can be reacted with acetonitrile in the presence of sulfuric acids (e.g., "103% H", S0 _A equivalents) and that The reaction product is then diluted with water. The product is 1,3-diacetamido-3,5 dimethyladaaantane which is obtained in form of white crystals. The reaction for the production of this substance can be represented as follows:

103% + 2CH ₃ CM H ₂ SO ₄

N-CCH, + ³

H ₉ O

HgC-C-N-

Including the desired product according to one of the above examples It is essential to obtain the acidic oil solution old one large amount of water to dilute for hydrolysis or Solvololye to enable the formation of the two amido groups runs "If the reaction mixture is diluted with enough water, the 1,3-diacetamido" 5,7 dimethyl

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adaaantan in the form of white crystals and can be filtered off .

According to another typical example, 1,3-dihydioxy-5,7-dimethyladainantane is reacted in the presence of fuming sulfuric acid with hydrogen cyanide which has been generated in situ by adding NaCN and a mixture of the diol and fuming acid. The mixture is then diluted with water and 1,3-Diformaraido-5,7dimethyladamantane is formed. In this case the diamido product is soluble in the aqueous sulphurous acid and does not fail. It can be extracted from it by a suitable solvent such as benzene or ether extra.

According to another typical example, 1,3-dichloro 5,7-dimethyladaiaantane is _{reacted with hydrogen cyanide in the presence of iauchendei sulfuric acid (e.g. n} 105% HoSO. " and iauchenden acid has been eizöugt * the mixture is then / rerdünnt with water and one obtains 1,3-Diformamido-5,7-dimethyladamantane ₃ in this case, the Diamidoprodukt in the aqueous sulfuric acid is soluble and does not fall out _c may dsraiis be extracted by a suitable solvent such as benzene or Xthe: <

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BAD ORiGINAL

The dihydroxy reactant used in the process according to the invention can be a diol of adamantane itself or of an alkyladamantane, with the adamantane core 1-2 alkyl groups with a total of 1-10 carbon atoms are located. The two hydroxyl groups can be attached to the bridgehead and / or non-bridgehead carbon atoms of the core. Examples of such reactants are the diols of the following hydrocarbons: AdamantaneJ 1-methyl- or 2-methyladamantane; 1 ethyl or 2-ethyladamantane; 1,2-dimethyl ° or 3, 3-dimethyladamantane; 1-methyl-3 ethyladamantane / Diftthyladamantane; l-n-propyl or I- isopropyladamantane? l "n" butyl adamantane; 1,3-di = n-pentyladamantane; 1-methyl-3-heptyladamantane? 1-n-decyladamantane. Such diols can be produced by catalytically oxidizing the corresponding Adamantane hydrocarbons are produced with air in such a way as in the on 10, 9 “1964 filed US application 395 580 or by reacting hydrocarbons with chromic acid, in the manner described in U.S. Patent Application 421,614 of 28c12.1964 has been described.

In the context of the process according to the invention, the dihalogen reactant can be a dibromo or di-

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act chlorine derivative of adamantane itself or an alkyladamantane in which there are 1 to 2 alkyl groups with a total of 1 to 10 carbon atoms on the adamantane core, the two halogen atoms are located on the adamantane core and can be on bridgehead and / or non-bridgehead carbon atoms of the core o Examples of such reactants are the dibromo * or dichlorodorivafce of the following hydrocarbons: Adamantanes 1-methyl- or 2-methy! adamantanes 1-ethyl- or 2-sthyladamantane; 1,2-dimethyl or 1,3'-dimethyladamantane;1-methyl-3-sthyladamantane; Dietadamantane ^ 1-n-Propyl »or 1-Isopropyladamantane ^ l = n-Butyladamantane? 1,3-di-n-pentyladamantane; 1-methyl 3-heptyladamantane ^ and ln-decyladamantane ·, Such dihalogen derivatives can be prepared by reacting the corresponding adamantane hydrocarbon with chlorine or bromine in the presence of AlCl ^ or AlBr ₃ , as described in German patent 1,101 410. Methods of production are also described by Stetter in "Angewandte Chemie * International Edition, Volume 1 (1962) No. 6, pages 287-288.

The other reactant namely the cyano compound can a hydrogen cyanide or an alkyl or aryl mononitrile with 2 to 20 carbon atoms. Preferred nitriles are

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• ic ·

Acetonitrile and Benzonitrile »The following list are other examples: Propannitrii; Butannitrii; 2 methylbutanenitrile; Qctanonitrili Dodecannitrii; Octadecannitrii; o ~ tolunitrii; m < ethylbenzonitrile? p-Isopropylbenaonitrile benzyl cyanide, ¹ and benzylacetonitrile> If hydrogen cyanide is used as the cyano compound, it can be generated in situ by adding NaCN or KCN to a mixture of dihaloadamantane and fuming sulfuric acid.

In order to carry out the implementation of the dihydroxyadamantane compound or the dihalogenadamantane with the cyano compound, it is extremely important that the sulfuric acid has the highest possible acid concentration and is used in large quantities, since otherwise the reaction does not take place or only at one of the hydroxyl sites or Halogen = substituents of the adamantane compound. In other words, this means that the use of sulfuric acid of insufficient strength or in insufficient quantities does not lead to the sucking of the desired diasido compound and no product is produced or that only the monoamido derivative is obtained. In all cases, the concentration of the starting acid should be at least about 96% H ₉ SO, equivalent weight if the dihydroxyadamantanes are used as a reactant.

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partner and it is clearly preferable when using the dihydroxyadamantane or the dihalogen adamantane fuming heavy acid acid which has an H ₂ SO ₄ equivalent in the range of 100 to 1.10% by weight and in particular fuming acid in the range of 102 Use 106% H ₀ SO, en ^ Maximum yields of the desired product can easily be obtained by using fuming sulfuric acid »

The minimum proportion of sulfur in the adamantandio compound which can be used in the context of the orf induncingerotiosen process fluctuates! with the concentration of SchwofeIaBiUG .. If one concentrates "Schwf? ielsaui" (96TU ig) used for the ancestor of the invention, the moles of HoSO ^ equivalents should be used per mole of Adanantan diol compound 50; Exceed 1. In particular, this should. Excess ratio 100 t .1 to ensure that the bente yield of the desired Dianddo compound is obtained. When the acid concentration is 102% H ₂ SO ₄ , the minimum HgSO ^ .- diol ratio is about 1? : 1 and preferably this ratio is at least 22 s 1. Even lower _{H2SO d} : diol ratios are permissible if the acid concentration is increased to 105% H2SO4; ratios of at least 15: 1 are then

always preferred. ^r

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As stated above, when the cyano compound is reacted with the dihalogonadaraantane compound, smoking soltweens with a concentration of 100 to 110% HgSO ^ weight equivalents is used and the concentration of the fuming acid is preferably between 102 and 106% H ^ SO ^. the amount of the fuming Säuio should snin so that the Molvorhältnis of H ₂ sO ^ to de * Dihalogenadaniantan compound is at least 10; 1 and in particular at least 20: 1 arrows "

The amount of the cyano compound should be such that at least 1 molecule of it is available at the position each hydroxyl group or each halogenatoras to react, i.e. in other words that the molar ratio the cyano compound to the adamantane diol compound or the dihalocrenadamantane compound is at least * 2: 1 " An f) excess of cyan bond over this ratio is not harmful and ei η VeihSltnia of about 3: 1 can in tvT) are used in cases,

When performing dte ο · ί-induuciHi, -uif; i »r.cu process becomes the adamantanediol compound or dihalogsnadamantane Compound preferably in strong sulfuric acid first

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or dissolved in fuming sulfuric acid in such an amount that the molar ratio of H ₃ SO ₄ to the diol is at least the ratio given above and preferably above this range. This can only be done by adding the diol or the dihalo compound and sulfuric acid at room temperature and stirring for several minutes. If the compound goes into solution, heat can be released, but the exothermic reaction is relatively mild. In cases in which a dibronomer bond is used as the reaction partner, the resulting solution is deep red or maroon brown given in the above equation. This reaction can take place at any temperature between the freezing point of the reaction mixture up to its boiling point, e.g. be (minus) "20, conducted from to 8O ⁰ C, but it is usually done at about room temperature. If NaCN or KCN is used to generate KCN in situ as the Cyanreaktionspartner, the temperature in general, be maintained substantially below 26 ⁰ C "should be to prevent HCN boils off or the reaction should be under pressure

009831/1803 'bathroom ORiGiNAL

carried grazing. With HCN or RCN as cyanide action partner, the reaction will generally be complete within 30 minutes of reaction time.

When the first phase of the overall action has been completed, a relatively large volume of water is added to the mixture in order to hydrolyze or soften and produce the desired diamido product. This is preferably done by pouring the strongly acidic mixture on gastro3senos ice to cause a thinning and at the same time to prevent the temperature from rising to an undesirably high value Reduce sulfuric acid in a corresponding way so that hydio lysis or solvolysis takes place and the diamido product fails with the exception of the cases in which the di foraamido product (s), as mentioned above, tend to be soluble in the dilute acid. In general, the Concentration of the dilute acid must be less than Sofc BLSO, and in particular less than 20% . After this final reaction Beendi supply can Diamidoprodukt be filtered from the mixture, or in the case of Diformamidoprodukten the separation can be effected a suitable hydrocarbon or ether by extraction old _D

009831/1803 ^ _n .... - j

The following examples serve as an explanation finding,

example 1

To 50 ml of fuming sulfuric acid with a concentration of 102% H ₂ SO ₄ Gowichtsäguiralenten, which have been ^{cooled to about 10 0} C, 5.0 g (0.0? 5 mol) of 1,3-dihydrocyty 5.7 Dinuithyladaiaantan in pulveiisiertei Foim ge and the Minuhung vuido qethtt um dar? Diol in the sliun; 7, v ltt.'iftn- Sine voi l.'stiindit ^ Lössung tand

in «itwa fi Miiun.öii tsiati Dan Molvo ^] ·. · 1] inii. \ f> ii H ₄₁ SO. · ";; iciii on to the Dj.ol LetiUti about 3H: I The Wi.sphmni was l> ei about] 0 ° C, held and stirred, while 4.1 y (0.10 mol) acetone slowly in the course of 30 The mixture was then added for a further 45 minutes to ensure that the reaction was complete. The ratio of acetonitrile to the diol was approximately 4: 1 0.5 kg), whereupon the egg melted and the resulting dilution of the acid solution caused hydrolysis, in the course of which the diacetamido product was finely distributed in the form of a

009831/1803 BAD OWGINAL

Precipitation formed. The mixture was filtered and the residue was washed with acetone and dried. A white crystalline product was obtained in an amount of 6.75 g. This product was analyzed by vapor phase chromatography, infrared analysis and nuclear magnetic resonance analysis to be essentially pure 1,3-diacetamide · 5,7-dimethyladamantane. It had a melting point of 315 ° C. and its yield was 95%, calculated according to the theory. This example also shows that the use of a H «SO ^: diol molar ratio of 38: 1 for fuming sulfuric acid with 102% H ₂ SO ₄ equivalents gives an excellent yield of the desired Diamido product results o

Example 2

This example shows the precipitation of 1,3-diformamido-5,7-diaethyladantantane and was generally used in the Performed the same way as the previous example except that powdered RaCN was added to the Acid-diol solution was added instead of acetonitrile., The NaCN was in an amount of

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~ 17

7.5 g and it was reacted with the sulfuric acid to form HCN, which in turn reacted with the diol in the manner described here. The molar ratio of the HCN produced to the dimethyladamantanediol was about 6: 1. More heat was released during this reaction than in the case of acetonitrile and the temperature of the mixture tended to rise this reaction formed Na ₂ SO ₄ I and it tended to make the mixture gelatinous if a low temperature was maintained. As a result, after all of the NaCN had been added, the temperature was allowed to rise to room temperature and the mixture was stirred for half an hour. After dilution as in Example 1, the diformamido product was formed, but it remained in solution. It was extracted therefrom with a 50:50 mixture of ether and benzene, the resulting solution was washed with water and then _{dried over Na 2} SO 4 and the solvent was evaporated. The resulting product had a melting point of 185 ° C. and was identified by VPC, IR and NMR as 1,3-di-formaldo -5,7-dimethyladamantane. The yield, based on theory, was about 85% "

BAD OFHGlHAL 009831/1803

Example 3

Example 2 was repeated except that HCN itself was added to the acid and the Diolgenisch Realetionsteaperatur was maintained at about 10 ⁰ C until the reaction was complete and 1,3-dimethyl -5,7 Difonaaraido adamant in a yield τοπ about 95%, based on theory was obtained.

Example 4

The diacetamido "compound of Example 1 was prepared again but concentrated sulfuric acid (96% HaSOj) in a large amount in place of smoking" of the acid used * Specifically were 0.47 q (0.0024 mole) of l, 3 ~ dihydroxy ~ 3,5-dimethyladamantane suspended in 2.5 ml (0.048 mol) of acetonitrile and the mixture was stirred and treated with 10 al of concentrated sulfuric acid, which was added all at once. The molar ratio of H ^ SO _11, to diol was about 68: 1 "The molar ratio of acetonitrile to diol was 20: I ₁ Ss held a highly exothermic reaction mixture was then diluted the mixture with a large volume of water and the sulfuric acid by Zuga -

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be diluted by aqueous NaOH, a white precipitate being obtained * The product was impure 1,3-diacetamido-5,7-dimethyladamantane and had a melting point of 305 ± 308 ⁰ C ₀ be purified by recrystallization from N, N ^{rdimethylformamide,}

Example p

Another approach was essentially as in the example 4 made using concentrated sulfuric acid except that the molar ratio of HoSO. au diol was reduced to 34: 1 and the molar ratio of acetonitrile to diol was 40: 1. Under these conditions, no diacstaraido product was obtained »This shows that a 96% igp H "SO. and a molar ratio of H ^ SO ^ au diol of 34: 1 is not sufficient to cause a reaction both hydroxyl positions of the dihydroxyadamantane compound only achieve-

Example 6 This example shows the preparation of 1,3-dibenzamido-

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5.7 -dimethyladamantan by a method of Example 1 analogously to the au · jenigen but with replacement of the benzonitrile with acetonitrile "3 g (0.0153 mol) were Dimethyladamantandiol in 30 ml of fuming sulfuric acid (102% H ₀ SO.) And 5 g (0.0459 mol) benzonitrile dissolved bssWn was added dropwise with stirring to the cooled mixture o The molar ratio of H ₉ SO _A equivalents to Did was 38: 1 and that of benzonitrile to diol was about 3: 1 ~ The mixture was knocked out Poured ice and insoluble dibenza aido product formed. The mixture was filtered and the residue was washed with methanol and acetone and then dried, 5.8 g of the white crystalline product were essentially pure 1,3% dibenzamido-5,7-diaethyladaniantane. The yield, based on theory, was 94% and the product had a melting point of 250-251 ° C.

When adamantanediol or diols of other alkyl adamantanes as indicated here were used in place of 1,3-dihrodroxy-5,7 "diaethyladamantane, the same results as in the previous examples were obtained. In the same way, essentially analogous results were obtained Results when other cyano compounds take the place of

bath

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■■ - 21

le of the above-mentioned HCN, acetonitrile or benzonitrile to carry out the method according to the invention were turned o

Example 7

35 al of fuming sulfuric acid having an acid concentration of 103% HJSO.-equivalent weight, which was cooled to about 10 ⁰ C _0, 3.22 g (0.01 mol) of?, "" Dibromo-5,7 "dimethyladaraantan in powdered Form added and the mixture stirred until the dibromo compound had dissolved in the fuming acid. The resulting solution was deep red or chestnut colored _c The molar ratio of H ₂ SO ^, equivalent to the dibromo compound is about 68: I ₀ The mixture was at about 10 ⁰ C unaffected held _0, while 2.1 g (0.05 mol) of acetonitrile was added slowly over 15 minutes, and the mixture wei "tere stirring for 30 minutes to ensure the completion order represents reaction. the molar ratio from acetonitrile to the dibromo compound is about 5: 1 "The reaction mixture is then slowly poured over 300 g of crushed ice, whereupon the egg melts and the resulting thinning of the acid solution causes hydrolysis

009831/1803 BAD

runs off with formation of the diacetamido product in the form of a finely divided precipitate. At. This reaction with water changes the color of the mixture to light amber. The mixture is filtered and the residue is washed with acetone and dried. The product is kept in a white crystalline product in an amount of 2.56 g. This product is determined by vapor phase chromatography. Determined. In frarot · »and nuclear magnetic Rösonanzanalyse, as a substantially pure 1,3-diacetamido 5.7 dim" thyladamantanο It has a melting point of 315 ⁰ C and fell in a yield of 92%, based on the theory,

Example 8

This example shows the preparation of 1,3 difonaamido'5, 7-dimethyladamantane., Ea is carried out in general in the same manner as in Example 7, with the difference that powdered NaCN is added to the acid solution of the dibromo compound instead of acetonitrile ^ the NaCN 7.5 g is added over 2 hours. It reacts with the sulfuric acid to form HCN, which in turn :: t v.t with the D ^v Ibrom compound as described herein Weiae vas' The

00983

· "/ IO ~

The molar ratio of the HCN produced to the dibromodimethyladamantane is about 6: 1. During this reaction, flour is released from heat than is the case with acetonitrile and the temperature of the mixture tends to rise. In this reaction, Na ₉ SO. , and the mixture tends to become qelatinos if a low temperature is maintained. As a result, after adding the total NaCN, the temperature is allowed to rise to room temperature and the mixture is stirred for half an hour with the aid of a 50:50 mixture of ether and benzene, the resulting solution being washed with water and then dried over NaSO, and the solvent evaporated. The solid product has a melting point of 185 ° C. It is through VPC , IR and NMR identified as 1,3-difo »mamido 5,7-diaethyladamantane. The yield is about 85%, based on theory.

Example 9

When example 8 is repeated with the difference that HCN itself is the acid solution of 1,3 dibromo ~ 5,7-dimethylada ~ mantans is added and the reaction temperature up

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about 10 ⁰ C is kept until the reaction is complete, 1,3 «Diformamido ~ 5,7> dimethyladamantane is obtained in a yield of more than 90%, based on theory»

Example 10

When repeating example 7 with the difference that Benzonitrile is used instead of acetonitrile, 1,3-dibenzamido 5,7-diroethyladamantane is obtained in one Yield greater than 90%, the product is a white one crystalline powder with a melting point of 250 - 251 ° C.

If instead of 1,3-dibromo-5,7 «dimethylada» antan dibromo adamantane or dibromo derivatives of other alkyl adanantanes, as indicated herein, results similar to those in previous Examples 7-10 can be obtained. In the same way, if the corresponding dichloro derivatives are used instead of the DiW compounds get essentially the same results. Furthermore, if cyano compounds of the above »

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given type instead of HCN, acetonitrile or benzonitrile used for the inventive method essentially analogous results are achieved »

The Diamidoadamantan-compounds prepared by the process of this invention can in Diamidoadamantane acid "or base hydrolysis be converted, said compounds are polymerized with diacids Ki ~ nen" Accordingly find the erfindungsgemSss substances prepared using u _o a »amides in the production of poly" which can be used for the production of fibers, films and moldings.

The diaiaido adamantane compounds are also useful because they can be incorporated into polyoefins such as polyethylene or polypropylene and as antistatic substances for Fibers or molded articles act as lubricants when the polymer is extruded into a film. The usage of slip substances in polymer extrusion processes advantageous because they facilitate the extrusion process and result in a smoother pressed product «,

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So far, according to Stetter and Wulff, Chem.Ber «, Volume 93, Page 1366 (1963) 1,3-Diacetamidoadamantan from a mixture of 1,3 Dibromadamantan, Silbeiaulfafc and A «eto nitrile produced in the presence of concentrated sulfuric acid. This diacetomido product does not have any alkyl groups contains, has two unsubstituted bridging carbon atoms in the adamantine core and, as a result, contains *. its two tertiary hydrogen atoms per molecule these tertiary hydrogen positions are relatively reactive places »In contrast to this, the 1,3-D! amido-5,7-dialkyl produced according to the invention adamantane does not have any unsubstituted bridgehead carbon atoms and consequently no tertiary hydrogen atoms. This is advantageous when using this Diamido product <5 for the production of polymers, as polymers made from the diamine, which is derived from 1,3 "diamido-5,7-dialkyladamantanes derived, are more stable than the corresponding polymers would be if the two alkyl groups would not be present in monomer. In other words, this means that the presence of alkyl groups on the 5- and 7-positions of the adamantine core to a higher one Stability in terms of resistance to oxidation, thermal degradation and the like.

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» 27 -

The method Yorliegende but Preparation of 1,3-diamido adamantane is significantly advantageous over the method for producing 1,3-γοη Diacetaaidoadamantan which has been described in the above literature, because the present method does not use the expensive ▼ erhSltnismSssig Silbersalses requires, which is the case with the known method. It is also advantageous because higher yields of the diaaido product can be easily achieved. For example, the known process gives a yield of 70% of theory, while the process according to the invention easily achieves yields in the range of 9CTl of theory or more.

Claims

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Claims (5)

Patent claim 1. Process for the preparation of 1,3-diamidoadamantane compounds the general formula 0 H A. H 0 It - N - N HC • C wherein A is a group with an adamantane core and R is a hydrogen atom and / or a hydrocarbon radical having I to 19 carbon atoms, namely an alkyl, phenyl, alkaryl or aralkyl group, characterized in that one is a dihydroxyadamantane or a Dihydroxyalkyl adamantane with 1 to 2 alkyl groups on the nucleus, which contain 1 to 10 carbon atoms or in dibtom bs5w “dichlorides * i vat of adamantane or of alkydamantane in sulfur satire del concentrate j on of 96-110% H« SO, weight equivalency, vorzuvi A total of 102 10 (5? »H ^ SOj - weight equivalents, a molar ratio of H« S0 ^ zxi of the Adaraantan bond of at least 10: 1 and the mixture with HCN or RCN, where? in R a Kohlenwas aerstoffreut mil 1 to 19 carbon atoms untei maintaining a Molveihaltni.ssös the cyano compound of adamantane au compound of at least 2 s 1 \ uas "t ^ t _r after which the Reaktionbyemisoh wit water verBötssi 'ad I., 3 Diamidoadaiuantan au »dom öemis» it jüt jierto - —_ 00 9831/1801 ^8AD 2o method according to claim l _r, characterized in that the sulfuric acid is used in a molar ratio to the adamantanediol compound of 50: 1, preferably 100 ι 1 » 3. The method according to claim 1 or 2, characterized in that g e that one has the sulfuric acid in a molar ratio to the dihaloadamantane compound 10: 1, preferably 20: 1. 4 "Process according to claims 1 to 3 _f, characterized in that the cyano compound RCN used is a compound in which R is an alkyl group, in particular acetonitrile or benaonitrile" 5 “The method according to claim 1 to 4, characterized in that a dihydroxyalkyladamantane with 1 to 2 alkyl groups on the nucleus and 1 to 10 carbon atoms is used as the starting material. β. Process according to claims 1 to 5> characterized in that a sulfuric acid with 100 to 105% H ^ SO ^ equivalents is used 00983 1/1803 bad original