CH502973A - Coupling adamantane groups by 3-4C polyethylene bridges by (a) forming a soln. of (I) a 10-20 C adamantane or alkyladamantane contg. at least one unsubstd. brid - Google Patents

Abstract

Coupling adamantane groups by 3-4C polyethylene bridges by (a) forming a soln. of (I) a 10-20 C adamantane or alkyladamantane contg. at least one unsubstd. bridged main C atom, and no tert. alkyl C atom, and (II) a 3-4 C alkyl chloride or bromide, in a molar ratio relative to hydrocarbon greater than 1:1, but below 2:1, (b) maintaining the soln. at -20 to 50 deg.C while AlCl3 or AlBr3 is mixed with the soln. until the greater part of the adamantane hydrocarbon has reacted, and (c) recovering the pdt. contg. adamantane groups linked by 3-4 C polymethylene bridges between bridged main positions. The method enables linear and crosslinked polymers to be produced, as well as pdts. of the bis-type. The bis-type products can be converted of monomers useful for prodn. of new polymers, such as polyesters and polyamides.

Description

  

  
 



  Method for linking adamantane rings by C3 or C4 polymethylene chains
This invention relates to a method of linking adamantane rings by (IB or C4 polymethylene chains. In this way, novel compounds can be prepared which have 2 or more adamantane rings in the molecule.



   The starting adamantane hydrocarbons have 10-20 carbon atoms and consist of adamantane or an alkyladamantane hydrocarbon with at least one unsubstituted bridgehead carbon atom, the alkyladamantane not having a tertiary alkyl group as a substituent.



   The cage-like structure of the adamantane ring can be represented in various ways, e.g. B. by the following formula:
EMI1.1

This formula shows that the adamantane ring consists of 3 condensed cyclohexane rings, which are arranged in such a way that there are 4 bridgehead carbon atoms of equal value. The preparation of methyl- and / or ethyl-substituted adamants by isomerization of tricyclic naphthenes with aluminum halide or an HF-BF3 catalyst has been described in various places: Schneider US Pat. No. 3,128,316; Janoski et al.

  U.S. Patent No. 3,274,700; Schleyer et al., Tetrahedron Letters No. 9, pp. 305-309 (1961); and Schneider et al., JACS, Vol. 86, pp. 5365-5367 (1964). The isomerization products can have the methyl and / or ethyl groups connected to the adamantane ring either by bridgehead position or without this or by both types of bond, although the termination of the isomerization promotes bridgehead substitution.

  Examples of such alkyladamantanes which have been prepared by isomerization are methyladamantanes, dimethyladamantanes,> 2ithyladamantanes, methyl ethyladramantanes, dimethylethyladamantanes, trimethyladamantanes and tetramethyladamantanes.



   The production of adamantane hydrocarbons, which have higher alkyl groups, was described by Spengler et al., Erdöl und Kohl-Erdgas-Petrochemie, Vor. 15, pp. 702-707 (1962). These authors used the Wurtz synthesis, i. H. the reaction of l-bromoadamantane with alkali alkyls to replace the alkyl group for the bromine substituent. In this way, 1-n-butyl adamantane and 1-n-hexyl adamantane were produced.



   Recently, Hoek et al., Recueil Volume 85 (1966), pages 1045-1053, described another way to prepare butyl-substituted adamantane. This process comprises the reaction of 1-bromoadamantane or 2-bromoadamantane with thiophene using SnCl4 as a catalyst in the presence of an excess of thiophene as solvent to form adamantylthiophenes, which are then hydrogenated to the butyl-substituted adamantanes.



   Gerzon et al., J. Med. Chem., 6, 760-763 (1963), and Gerzon U.S. Patent No. 3,096,72 discovered reactions of adamantane. Adamantane was reacted in a relatively large amount of cyclohexane with t-butyl chloride, which contained an AlCl3 promoter.

  Under the reaction conditions used, the main reaction consisted of a hydrogen / chlorine change between the two starting materials, with the formation of l-chloroadamlantane. There is a certain similarity between the starting materials of this process and the starting materials of the process according to the invention, but, as will be described later, there are fundamental differences between the reaction conditions and end products; the reaction proceeds in a different way so that a linkage of adamantane rings occurs.



   The present invention relates to a process for converting adamantane hydrocarbons into new products which can have 2 or more adamantane cores per molecule which are linked to one another by C8 or Cl polymethylene chains. Products which have only two linked adamantane nuclei can be prepared either from 1,3-disubstituted propanes or 1,4-disubstituted butanes, the substituents corresponding to the starting adamantane hydrocarbons or such hydrocarbon atoms, but also 1 or 2 halogen atoms own as bridgehead positions.

  According to the invention, it is also possible to produce new polymer products which have more than 2 adamantane rings which are linked to one another by C8 or C4 polymethyl chains. They are linear and cross-linked polymers. The process comprises the reaction of starting adamantane hydrocarbons with a C8 or C4 alkyl chloride or bromide in the presence of ASC13 or Als3.



   The process according to the invention is characterized in that a) a solution of 1. a Ct0-C20-adamantane hydrocarbon, consisting of adamantane or an alkyladamantane, with at least one unsubstituted bridgehead carbon atom, wherein the alkyladamantane has no tertiary alkyl group as a substituent, and 2. from a C3-C4 alkyl chloride or bromide in which the molecular ratio of alkyl halide to adamantane hydrocarbon is more than
1: 1 but less than 2:

  : 1, when the alkyl halide is tertiary butyl halide, and where the alkyl halide is a primary or secondary alkyl halide when the hydrocarbon is adamantane, b) dissolves in this solution at -200 C to + 500 C A1Ci3 or AlBr3 and stirs until the The main part of the adamantane hydrocarbon has reacted, the reaction temperature being higher than 100 C if the alkyl halide is tertiary butyl halide, and c) the product isolated from the reaction mixture, in which 2 adamantane rings are linked between bridgehead positions by a C3-C4 polymethylene chain.



   The reaction conditions are preferably such that the reaction mixture is homogeneous.



   The process can be regulated to increase the production of disubstituted propane or butane or to obtain mainly polymeric products with a greater number of adamantane rings per molecule.



   For the sake of simplicity, the products with 2 adamantane rings should be referred to as bis-products and those with more than 2 adamantane rings as polymers.



   The bis-products include both compounds which do not contain a halogen atom and halogen derivatives thereof which have 1 or 2 halogen atoms.



  These products correspond to the following formula: X-A (CH2) 11-A-X wherein A is an adamantane ring with 0-3 alkyl substituents, X is a bridgehead substituent consisting of chlorine, bromine, alkyl with no tert. C atom or hydrogen, and n is 3 or 4. The total number of carbon atoms in each -A-X part is 10 to 20.



  If the starting adamantane hydrocarbons have 2 or more unsubstituted bridgehead positions, in many cases the majority of the bis-product obtained consists of the dihalo product in which each X substituent of the above formula is chlorine or bromine. If you z. B. reacting n-butyl chloride with 1-ethyladamantane under conditions which mainly lead to the formation of bis-products, the main component will generally be the following compound:
EMI2.1

As a rule, the bis-product will also contain substantial amounts of the corresponding monochlorine compound and also of the corresponding hydrocarbons.

  In a similar manner, bis-products with a trimethylene linkage instead of a tetra methylene linkage can be prepared if n-propyl chloride is used instead of n-butyl chloride.



   Polymeric compounds which can be prepared according to the invention include linear and crosslinked products, largely dependent on the number of unsubstituted bridgehead positions in the adamantane hydrogen. For example, if the starting hydrocarbon is 1,3-dimethyladamantane, only the linear compound is obtained. Such polymers have the following structure when a C1-alkyl halide was used for the linkage:
EMI2.2
 Using 1-ethyl-3-methyladamantane usually results in an analogous polymeric compound having one ethyl group in place of the one methyl group in each ring.

  For the preparation of such linear polymeric compounds, the starting adamantane hydrocarbons must in particular have two unsubstituted bridgehead carbon atoms in the core. On the other hand, if the starting hydrocarbons have 3 or 4 unsubstituted bridgehead positions, interchain crosslinking via the tri- or tetramethylene bonds between the adamantane cores in each chain can result in the crosslinked polymers.

  Examples of adlamantane hydrocarbons from which the crosslinked polymeric compounds can be prepared are
Adamantane, 1 -ethyladamantane,
2-methyladamantane,
1-ethyl-2-methyladamantane,
1-ethyl-4-methyladamantane, further any of the dimethyladamantane isomers or the trimethyladamantane isomers or ethyldimethyladamantane isomers in which not more than one of the alkyl groups is in a bridgehead position, n-hexyladamantanes, n-decyladamantanes and the like.

 

   In general, both types of these polymeric products can be made in the same process. The nature of the main reaction product depends on the amount of hydrocarbon in the tank, further on the proportions of the alkyl halides used, whether the alkyl halide is primary, secondary or tertiary, and on the reaction temperature. The adamantane cores are linked by Ca or C4 polymethylene chains and they consist of either bis-products or polymers or a mixture of these compounds.



   In a typical embodiment of the process according to the invention, 100 moles of 1,3-dimethyladamantane are dissolved in 150 moles of t-butyl chloride.



   Mix at room temperature and add small amounts (each 0.5 mole) of AlCla over 2 hours to a total of 5 moles. The aluminum chloride goes into solution and gaseous hydrogen chloride and isobutane are released, but no separate catalyst complex is formed. After the reaction has progressed sufficiently, the reaction mixture becomes solid. The main reaction can be expressed by the following equation (hydrogen atoms are not indicated):
EMI3.1

Under these conditions (molar ratio of t-butyl chloride to adamantane = 1.5. 1 and temperature about 250 ° C.), substantial amounts of a bis product are obtained.

  The main component of this bis-product is 1,4-bis (3-chloro-5,7-dimethyl-1-adamantyl) butane, as shown in the reaction equation, and has a melting point after purification of 215-217 C. In Other bis-products, which may contain chlorine, are obtained in smaller quantities. They are represented by the following formulas:
EMI3.2

EMI3.3
 By chromatographic analysis, these three bis-products were identified as three different peaks, with the dichloro compound in the bulk. It is noteworthy here that the t-butyl chloride, which provides the linking part of the product, is branched, but the compound is formed unbranched.

  If t-butyl halide is replaced by n-butyl, isobutyl or sec. Replaced butyl chloride or bromide, the same 1,4-disubstituted butanes are obtained. If 1-ethyl-3-methyladamantane is used instead of 1,3-dimethyl-adamantane, the main product is 1,4-bis (3-halogen-5-ethyl-7-methyl-
1-adamrantyl) butane.



   In the same way, with n-propyl or isopropyl halides and 1,3-dimethyladamantane under the reaction conditions mentioned above, bis-products, which are 1,3-disubstituted propanes, and otherwise the same products mentioned above, can arise. In general, the main product is the dihalo-bis product, namely 1,3-bis (3-halo-5,7-dimethyl-1-adamantyl) propane. In the same way, 1,3-bis (3-halo-5-ethyl-7-methyl-1-adamantyl) propane can be obtained as the main product by using 1,2-ethyl-3-methyladamantane instead of 1,3-dimethyladamantane .

  While the above description indicates the use of tertiary halides, in practice the primary or secondary alkyl halides are more advantageously used. Tert. Butyl chlorides or bromides will generally only yield bis-products under certain conditions; in particular, they tend to cause bridgehead halogenation of the adamantane ring, as indicated in US Pat. No. 3,485,880. Linking of the adamantane rings is usually much less common.



  To a linking reaction via tert. To effect butyl chloride or bromide, it is important that 1. the temperature is in particular 10 to 500 C, preferably 20-40 C, and 2. that the molecular ratio of the tert. Butyl halide to adamantane hydrocarbon is less than 2: 1, but more than 1: 1. It is also important that the adamantane hydrocarbon be an alkyl adamantane and not adamantane itself, since the linkage of the latter can only be effected with a primary or secondary alkyl halide.



   If the starting hydrocarbon has 2 or more unsubstituted bridgehead positions and the alkyl halide is a primary or secondary chloride or bromide, a major amount of bis-products can be obtained if a molar ratio of alkyl halide to starting hydrocarbon of 1: 1 to 3 1 is used. On the other hand, the formation of the polymeric compound is favored if the ratio is increased, namely if it is more than 3: 1, namely 6-20 1.



   If the starting hydrocarbon only has an open bridgehead position, only a bis-product without halogen can be obtained. So z. B. by reacting l-ethyl-3,5-dimethyladamantane with iso- or n-propyl chloride or bromide under the reaction conditions of the present process, only the following compound is obtained:

  :
EMI3.4
 In another example, if one uses a tetramethyladamantane which has only one of its methyl substituents in a non-bridgehead position, namely 1,3,5,6-tetramethyladamantane, one generally obtains an isomeric compound of the hydrocarbon shown above, but with one bridgehead and one non-bridgehead methylene group for each sithyl group. These hydrocarbons and other bis-products can be produced in the form of high melting point solids by the present process.



   It is an important feature of the process for the preparation of bis-products or polymeric compounds that a homogeneous system is established and maintained during the reaction without a substantial amount of a separate catalyst phase being formed. Aluminum chloride or aluminum bromide most likely react in the reaction mixture with the alkyl halide and form a complex which can at least in part serve as an active catalyst. However, it is more likely that dissolved aluminum chloride or aluminum bromide represent the catalyst and that, in the case of aluminum chloride, the complex formed is necessary in order to bring the aluminum chloride into solution.

  In any case, it is necessary to carry out the process according to the invention to bring about and to maintain a homogeneity by the fact that the alkyl halide content of the mixture is sufficiently high to keep the complex in solution and that no separate phase is formed. If the aluminum halide does not dissolve in the reaction mixture or if the catalyst precipitates out of the mixture as a complex, the catalyst mainly promotes a hydrogen-halogen exchange reaction and not the desired linkage reaction for the preparation of the bis-products or polymeric compounds. For example, when using large amounts of saturated hydrocarbon solvents, such as. B.

  Cyclohexane, the catalyst complex remains essentially undissolved in the mixture and forms a separate phase. This catalyzes the hydrogen-halogen exchange reaction and not the linkage reaction. This is one reason why when adamantane was used with t-butyl chloride in the presence of cyolohexane, l-chloroadamantane was formed rather than the linked product.



   Another reason that l-chloádamantane in particular is formed instead of the products of this process is based on the fact that tert is used as the starting compound. Butyihalide used together with adamantane. Tert. Butyl chloride or tert. Butyl bromide have a tendency to promote hydrogen-halogen exchange, and this tendency is much greater than that of the primary or secondary C3-C4 halides, and especially when the starting carbon is adamantane. It follows from this that if you use adamantane as the starting compound, only primary or secondary halides should be used, such as. B. n-propyl, isopropyl, n-butyl, isobutyl or sec-butyl chloride or bromide.

  To bring about a link, you can tert with alkyladamantanes. Use butyl halides if the molar ratio to A-y adamantane is 1: 1 to 2: 1 and the temperature is above 100 ° C., as mentioned above. In any event, it is best to carry out the reaction with either a primary or a secondary halide.



   From the reaction equation presented above it can be seen that when using tert.



  Butyl halide the connection between the adamlan- tane rings unexpectedly does not have a methyl group and only 1,4-disubstituted butane is obtained.



  In other words, normal, secondary and tertiary butyl chlorides or bromides usually all cause a tetramethylene bond between the adamantan cores.



   The process of the present invention is limited to the use of alkyl chlorides or bromides with 34 carbon atoms. The desired reaction products are not obtained when using ethyl chloride or bromide, not even when using alkyl halides having 5 or more carbon atoms. The ethyl halides are essentially inert under the reaction conditions of this process.



  On the other hand, the higher halides with 5 or more carbon atoms tend to form an insoluble Kataly satorschlamm and not the desired active complex, which would be in solution and could catalyze the reaction in the desired direction.



   The reaction temperatures for this process are in a range from -200 C to + 500 C. When using primary or secondary alkyl halides, a temperature of 0-300 C. is used in particular. For the preparation of polymeric compounds, a temperature of more than 150 should be used C work, especially at a temperature of 20-300 C. Only relatively small amounts of aluminum chloride or aluminum bromide are necessary for the course of the reaction, and it is generally desirable that the total molar ratio thereof in relation to the alkyl halide is less than 0.2 is, especially 0.001-0.1; one works best in the range of 0.005-0.1.

  The desired aluminum halide is preferably added to the mixture in small amounts during the entire reaction period with vigorous stirring. Hydrogen chloride and propane or isobutane are formed during the reaction. These are usually derived from the reaction system. In general, the reaction has ended after the reactants and the catalyst have been stirred for one hour.



   After the reaction has ended, methanol can be added to the reaction mixture with stirring in order to make the catalyst inactive. It is possible to work up the reaction mixture by known methods in order to isolate the end products. When bis-products are present, it is preferred to separate the monohalogen and hydrocarbon products from the dihalogen product and from each other by fractional crystallization using a suitable solvent such as carbon tetrachloride or methylene dichloride. If desired, the starting materials can be fed back into the reaction system in order to increase the yield of the dihalogen product.

 

  Polymeric products, if they are not too strongly crosslinked, can be dissolved in a solvent such as benzene. You can then separate fractions of different moles kuiargewichts from the solution by using a suitable anti-solvent, such as. B. acetone, added in certain amounts to cause a gradual precipitation.



   Preferred embodiments of the invention are described in the following examples. In most of the examples the starting hydrocarbon was 1,3 dimethyladamantane, abbreviated to DMA. The bis-products obtained therefrom have 0, 1 or 2 chlorine atoms per molecule and were designated in the following way for examples in which alkyl chlorides with 4 carbon atoms were used: 1.

  H- (DMA) - (CH2) 4- (DMA) -H
1,4-bis (3, S -dimethyl-1-adamantyl) -butane
II. Cl- (DMA) - (CH2) 4- (DMA) -H
1 - (3-chloro-5'7-dimethyl-1-adamantyl)
4- (3, 5) -dimethyl-1-adamantyl) -butane
III. Cl- (DMA) - (CH2) 4- (DMA) -Cl 1, 4-bis- (3-chloro-5,7-dimethyl- l-adamantyl) - butane The products were determined by the following analyzes: gas chromatography, IR, NMR and mass spectra. Analyzes of the reaction products in the examples below are given on the basis of alkyl chloride-free compounds.



   Example I.
This example describes the reaction of DMA with n-butyl chloride under reaction conditions which mainly lead to the bis-product.



  A mixture of 2.25 g (0.0243 mol) of n-butyl chloride and 2.00 g (0.0122 mol) of DMA (molecular ratio = 2.0) was stirred at 280.degree. 0.1 g of AlCl 3 was added. The aluminum chloride dissolved to form a homogeneous, yellow-green solution and vigorous evolution of gas occurred. After 7 minutes the solution became cloudy, after 12 minutes thick and opaque, and after 17 minutes it became solid with a precipitate. After 38 minutes the mixture could no longer be stirred. After 60 minutes, the mixture was stirred with 1 ml of methanol. A plastic mass was obtained.

  Complete solution occurred by heating with 4 ml of toluene, and by cooling; When the solution was brought to room temperature, vigorous crystallization was achieved. The gas chromatographic analysis of the entire reaction product is given in Table A below; the results are in Gb weight percent on a butyl chloride free basis.



   Table A.
Example 1 Example 2 (n-Butyl-C1; (n-Butyl-C1;
280 C) Oo C)
DMA 4.3% 0.4% 1-chloro-DMA 15.4 8.2 unknown A 1.1 1.0
1,3-dichloro-DMA 5.6 7.0 a-chlorobutyl-DMAe (some peaks) 8.8 9.0
Chlorobutyl DMA chlorides 0.4 none unknown B 0.2 2.9 unknown C 2.2 2.9
Bis-connection I 0.9 none
Bis Compound II 15.4 6.2
Bis-compound III 45.9 65.3 polymer none none
The results in Table A for Example 1 show that the reaction product consists mainly of the bis compound, namely the dichloro-bis compound III, 1,4-bis (3-chloro-5, 7-dimethyl-1-adamantyl) - butane.



   Example 2
The reaction mixture was essentially the same as in the previous example, except that 0.2 g of aluminum chloride was used.



  In this case the reaction temperature was 0 C.



  The reaction started slowly, and it appeared that the reaction was speeded up somewhat as the aluminum chloride slowly dissolves. No separate phase of the catalyst complex was formed. After 47 minutes the mixture solidified. It was left to stand at 0 C overnight and then worked up by trituration with methanol and filtered. The solid obtained had a melting point of 135 to 2000 C. It was easily soluble in toluene, even at 0 C.



  The gas chromatographic results of this example are given in Table A. It can be seen from this table that the bis-dichloro product is obtained with an even greater yield using a lower reaction temperature.



   Example 3
In this experiment, secondary butyl chloride (2.26 g), DMA (2.00 g) and 0.1 g AlCl3 were used at a reaction temperature of 0 ° C. The molecular ratio of alkyl chloride to DMA was again 2.0.



  The aluminum chloride dissolved very quickly to form a greenish, homogeneous solution and there was copious evolution of gas. After about 15 minutes the reaction mixture solidified. The mixture was left to stand at room temperature for 2 days, mixed with methanol and filtered. The residue was dissolved in toluene and analyzed by gas chromatography. The results are shown in Table B.



   Example 4
The alkyl chloride was here tert. Butyl chloride was used and the reaction with DMA was carried out at about 260 ° C. with a molecular ratio of alkyl chloride to DMA of 1.4. 100 g (0.609 mol) DMA and 80.4 (0.869 mol) tert were used. Butyl chloride at room temperature and normal pressure. To this mixture was added 0.5 g of aluminum chloride. The aluminum chloride dissolves immediately and evolution of gas occurred. The solution turned dark yellow. At 1 hour intervals, 0.5 g of aluminum chloride was added until the total addition was 2.5 g of A1C13. At this point in time, an abundant crystalline satin of the product occurred.

  Finally, 2.5 g of additional aluminum chloride (0.0375 mol total) were added and the thick mixture was stirred for a further hour. All of the aluminum chloride C went into solution, and no phase of the catalyst complex which had formed during the reaction separated out. The product was worked up as usual by adding 200 ml of water, then heated and the mixture stirred on a steam bath. The organic phase obtained was slightly yellow and had the consistency of a molasses-like liquid. A small sample was dissolved in toluene. The analysis results are summarized in Table B. The residue was mixed with 200 ml of methylene chloride, but not all of it dissolved.

  After washing the solution with 10% sodium hydroxide solution, the reaction product was crystallized by removing most of the solvent by heating. It was filtered and about 48 g of a high-melting solid were obtained. This substance was recrystallized three times from carbon tetrachloride, and a white, salt-like, crystalline product with a melting point of 215-217 ° C. was obtained. This product was essentially the dichloro-bis-compound III, which was described above.



   Table B.
Example 3 Example 4 (sec. Butyl-Cl; (t-Butyl-C1;
260 C) 260 C) DMA 1.3% 18.5% 1-chloro-DMA 11.0 39.4 unknown A 1.0 2.7 1,3-dichloro-DMA 6.3 3.4 chlorobutyl-J ) MA, (some peaks) 10.4 1.1 chlorobutyl-DMA-chloride 101.4 none unknown B none 0.2 unknown C 0.5 1.0 bis-compound I 3.2 3.9 bis-compound II 42.0 8.7 bis-compound III 24.4 21.1 polymer none none
The results of Example 3 show that sec-butyl chloride also provided the bis product as the major product of the reaction, but in this case the monochloro-bis-compound II was predominant, although considerable amounts of the dichloro-bis-compound III were also formed.

  A comparison of Example 4 with other examples shows that tert-butyl chloride gives a significantly lower yield of the bis-compound than does other secondary or normal butyl chloride.



  This compound also has the tendency to only form bridgehead chlorination products of the adamantane hydrogen approach. Accordingly, the tert-butyl chloride is the least preferred alkyl chloride for preparing the products according to the invention.



   It should also be concluded from the preceding examples that all bis-products (I, II and III) have unbranched compounds (tetramethylene) between the adamantane rings, regardless of whether a primary, secondary or tertiary alkyl halide was used in the reaction.



   Example 5
This example should show the course of the reaction between secondary butyl chloride and DMA (molecular ratio = 5.2). The products were reacted at 0 ° C. and after 2, 6 and 18 minutes, larger or smaller samples were taken for analysis. A specific mixture consisted of 0.901 g (0.00548 moles) DMA and 2.61 g (0.0282 moles) sec-butyl chloride. This mixture was in a reaction vial and was cooled to -80 ° C. in a low temperature bath. At this temperature, 0.2 g (0.0015 mol) of aluminum chloride was added to the mixture. There was no reaction.

  The ampoule was then placed in another bath at 0 C, the mixture was stirred, whereupon it turned a pale green color and the evolution of hydrogen chloride began. After 2 minutes, the vial was quickly cooled in a low temperature bath and a small sample was taken for analysis. The ampoule was placed in the second bath for an additional 4 minutes (6 minutes total) and a sample was again drawn in the same manner. The procedure was repeated and a third sample was taken in the second bath after the total reaction time of about 18 minutes. The analysis results are summarized in Table C.



   Table C.
Reaction of sec-butyl chloride and DMA OC sampling after minutes 2 6 18 DMA 0.4% 0.4% 0.1% 1-chloro-DMA 23.1 16.8 12.3 unknown A 1.8 1.5 1.0
1,3-dichloro-DMA 10.7 8.9 6.7 chlorobutyl-DMAe (some peaks) 27.0 31.5 29.1 chlorobutyl-DMA chlorides (some peaks) 10.7 13.3 12.7 unknown B 0.2 traces none unknown C 1.1 0.6 0.5 bis-compound I 9.0 13.0 21.3 bis-compound II 4.0 9.8 11.8
Bis Compound III 2.0 4.3 4.5
Polymer no no no
The information in Table C provides information about the reaction mechanism by which the adamantane rings are linked to one another by a polyalkylene bond.

  The first step in this reaction appears to be a hydrogen-halogen exchange between the DMA and an alkyl chloride through a carbon ion mechanism to form 1-chloro-DMA, which then reacts with the alkyl chloride to form a number of chlorobutyl-DMA. After a reaction time of 2 minutes, 37% of these isomeric chlorobutyl-DMA compounds are obtained. Some of these compounds apparently undergo a hydrogen-halogen exchange reaction to give chlorobutyl-DMA chlorides, which in Table C reach a maximum value after about 6 minutes (13.3%).

  It appears that these bis-compounds by implementing these different
Chlorobutyl-substituted intermediate compounds with 1 chloro-DMA are formed by a subsequent carbon ion mechanism. From Table C it can be seen that after a reaction time of 18 minutes the 3 bis-products make up 37.6% by weight of the reaction product, the bis-hydrocarbon I being the main product under the reaction conditions of this experiment.



  Another reaction would increase the yield of the Bis products as well as the relative proportions of the halogenated Bis compounds.



   Although a high molecular ratio (5.2) of alkyl chloride to DMA was used in Example 5, no polymeric compound was obtained. This is because the reaction temperature was low. It appears that a temperature above 0 C (e.g.> 150 C) should be used to obtain the desired polymeric product.



   Example 6
This example was carried out using an insufficient amount of n-butyl chloride. A separate phase of the catalyst complex was formed and this was to demonstrate the adverse effect of using an insufficient amount of alkyl halide. The molar ratio of n-butyl chloride to DMA was 0.28. A mixture of 2.0 g (0.0122 mol) DMA and 0.32 g (0.00346 mol) n-butyl chloride was added to 0.05 g aluminum chloride and this mixture was stirred at 280.degree. There was a slow evolution of hydrogen chloride, the aluminum chloride dissolved, and after a few minutes a yellow complex layer separated out.

  After stirring the mixture for one hour, it was hydrolyzed with water and then analyzed. The results are shown in Table D.



   Table D
Reaction of DMA with an insufficient amount of n-butyl chloride
Example 6
DMA 63.0% 1-chloro-DMA 30.0 unknown A 1.3 1, 3-dichloro-DMA 2.6
Chloralkyl-DMA 0.4 unknown B 0.2 unknown C 0.3
Bis compound I 1.8
Bis compound II 0.5
Bis-compound III none
The data in Table D show that the reaction did not essentially go beyond the hydrogen-halogen exchange of the formation of 1-chloro-DMA and that no substantial amounts of the bis-compound were obtained. The result is to carry out the reaction with a sufficient amount of the alkyl halide to obtain the aluminum citloride complex in solution.



   Example 7
Adamantane (1.00 g, 0.00734 mol) was treated with tert. Butyl chloride (0.847 g, 0.00915 moles) was reacted in essentially the manner described in U.S. Patent No. 3,096,372. Cyclohexane (3.5 mol) was used as the solvent for adamantane. The mixture was stirred at room temperature, and 0.05 g of aluminum chloride was added to this mixture. The aluminum chloride did not dissolve, but formed a yellow complex layer with slight evolution of a gas. After stirring for 15 minutes, a further 0.05 g of Als13 was added and the mixture was stirred for a further 90 minutes. The catalyst complex phase was a brown liquid, while the organic phase was yellowish in color. The latter was washed with water and analyzed.

  The results are shown in Table E.



   Table E.
Reaction of adamantane and t-butyl chloride in cyclohexane
Example 7
Adamantane 13.6% l-chloradamantane 77.6
1,3-dichloroadamantane 8.8
100.0
From the information in Table E it can be seen that under the reaction conditions of Example 7, adamantane does not give any bis-products. There was only a halogen-hydrogen exchange between the alkyl chloride and the bridgehead hydrogen atoms of the adamantane ring.



   Example 8
This example shows the reaction of n-propyl chloride with DMA at an overall molecular ratio of 4.1. The alkyl chloride is added to the reaction mixture in 2 portions. A mixture of 1.91 g (0.0243 mol) of n-propyl chloride, 2.0 g (0.0122 mol) of DMA and 0.05 g (0.000375 mol) of aluminum chloride was stirred at 260.degree. The added aluminum chloride dissolved and a yellow solution was obtained which evolved hydrogen chloride, became thick after about 10 minutes and finally crystallized. A portion of the n-propyl chloride (2.01 g, 0.0256 mol) was added and the suspension was stirred for an additional 2 hours and it appeared to be thicker. The reaction product was then mixed with excess methanol and filtered, and a solid which had a melting point of 160 to 1800 ° C. was obtained.

  A sample of this crude product was recrystallized twice from hot benzene to give a compound which had a melting point of 215-2220 ° C. Other samples were recrystallized twice from hot carbon tetrachloride to give a white powder with a melting point of 211-2230 C. This compound was the bis product.



  This product was not specifically identified but was most likely the dichloro compound 1,3-bis (3-chloro-5,7-dimethyl-1 damantyl) propane because of its high melting point. After evaporation of carbon tetrachloride of the combined filtrates from two recrystallizations, another solid was obtained with a melting point of 165-1750 C. This product appeared to be a mixture of the bis-hydrocarbon and the monechlor-bis compound (analogous to, or to I and II, supra).

 

   Example 9
In this example, isopropyl chloride (1.91 g) and DMA (2.00 g) were reacted together. The mixture of these compounds was mixed with aluminum chloride (0.005 g) and the reaction temperature was 0 C.



  After about 20 minutes, the reaction mixture became cloudy and thickened to form a shock. The mixture was stirred at room temperature for about an hour. After this time it became too thick to continue stirring. It was then triturated with an excess of methanol and filtered. A colorless powder with a melting point of 135-1620 ° C. was obtained. The melting point was increased to 188-1980 ° C. by recrystallization from carbon tetrachloride, and a second recrystallization from carbon tetrachloride gave a melting point of 200 to 2040 ° C. This compound constitutes the bis product but the average number of chlorine atoms per molecule has not been specifically determined.

  This reaction (alkyl chloride: DMA molecular ratio = 2.0) gave essentially no polymeric product.



   Example 10
This example includes the reaction of isopropyl chloride with DMA. The molecular ratio was 4.2 so that bis-products and polymeric compounds could be formed. The reaction mixture consisted of 4.00 g (0.051 mole) isopropyl chloride, 2.00 g (0.0122 mole) DMA, and 0.16 g aluminum chloride. The reaction vessel was provided with a reflux condenser in order to feed the isopropyl chloride formed during the reaction back into the reaction mixture. The reaction was started at 0 ° C. and after 5 minutes the mixture was heated to 260 ° C. Vigorous evolution of hydrogen chloride occurred and after 10 minutes the reaction mixture turned into a yellow solid. After 20 minutes, the mixture was heated to 400 C.

  Hydrogen chloride was still evolving and isopropyl chloride was returned by reflux. After a reaction time of 45 minutes, the mixture was quickly heated to 800 ° C., 20 ml of methanol were added and the mixture was refluxed. About 2.30 g of a colorless, methanol-insoluble product were obtained. It was recrystallized twice from hot toluene, and about half of a residue was obtained which had a melting point of 237-2410C. This material could not be eluted from a high-temperature gas chromatography column and was the polymeric product. The material soluble in toluene was recovered from the filtrate by evaporation of the toluene and was a viscous liquid that tended to be at room temperature to crystallize.

  It was found by gas chromatography that this compound was largely composed of the bis-product of Example 8.



   Example 11
A mixture of 1.00 g (0.00609 mol) of l-ethyladamantane and 4.00 g (0.0509 mol) of n-propyl chloride was mixed with 0.03 g of aluminum chloride at 260.degree. The aluminum chloride dissolved, the solution turned yellow, and copious amounts of hydrogen chloride evolved. The mixture became thick and almost firm. After one hour, 0.89 g (0.0113 mol) of n-propyl chloride and 0.03 g of aluminum chloride were also added to the mixture. Gas continued to evolve from the solution and the mixture became thick. The resulting mixture was dissolved in methylene chloride, then methanol was added to it, to give a gummy product.

  The latter was triturated with methanol, and the resulting solid was isolated from the mixture by filtration and then dried. This substance mainly consisted of the bis compound, but also contained smaller amounts of chlorinated ethyladramantane. With a melting point microscope the following behavior could be determined:
1/5 melts at <910 C 1 /, melts at 91-1440 C 5/5 melts at 144-1790C
Example 12
This example describes the production of a polymeric substance from n-butyl chloride and DMA (molecular ratio 4.4) at 260.degree. The starting mixture consists of 5.00 g (0.054 mol) of n-butyl chloride, 2.00 g (0.01218 mol) of DMA and 0.05 g of aluminum chloride.

  First there is a violent evolution of hydrogen chloride, which then slowly decreases. Three more 0.05 g portions of aluminum chloride are added over one hour and the solution is left to stand overnight. A viscous solution resulted, but no separation of the catalyst complex took place and no crystalline product was obtained either. Mixing the solution with methanol gave a gummy precipitate which was separated, triturated with more methanol and then dissolved in benzene. A rather opaque solution emerged. This was filtered through diatomaceous earth and acetone was added to give a rubbery layer. This was rubbed with more acetone, producing grains.

  After evaporation of the acetone, a pale yellow polymeric compound was obtained which had a melting point of almost 1000 ° C. and which became opaque after cooling. This substance, which represented about 1/3 of the reaction product, had a molecular weight (osmometric) of 1186 and corresponded to the following formula:
EMI8.1
 Evaporation of the benzene-methanol layer gave an oily polymeric compound which had a low molecular weight and was Vs of the reaction product. This compound could not be crystallized.

 

   Example 13
This example describes the production of crosslinked, polymeric compounds from adamantane and n-butyl chloride. The latter is added in portions to the reaction mixture. A starting reaction mixture consisted of 1.1 g (0.0081 mole) adamantane, 2.2 g (0.024 mole) n-butyl chloride and 0.05 g aluminum chloride. This was stirred at 260 ° C. during which it became homogeneous and hydrogen chloride evolved.



  After 20 minutes the solution was quite viscous and the evolution of hydrogen chloride slowed somewhat. At this point in time, 1.77 g (0.019 mol) of n-butyl chloride were added, with vigorous evolution of hydrogen chloride again taking place and the mixture remaining homogeneous. Addition of 0.88 g (0.0095 mol) of n-butyl chloride caused the reaction to stop. A viscous solution remained. A clear film was left after evaporation of butyl chloride from a small sample. An additional 0.01 g of aluminum chloride was stirred into the reaction mixture, foaming occurring and the mixture becoming solid and rubber-like.

  Trituration with methanol and stirring gave a suspension of hard, colorless particles which were separated off by filtration and dried. Microscopic determination of the melting point of this product showed that the morphology did not change when heated up to 3500 ° C. This suggested that a crosslinked polymeric compound was obtained.



   Example 14
Adamantane and n-propyl chloride were converted into a crosslinked, polymeric compound in the same way. 1.0 g (0.0073 mol) of adamantane, 5.80 g (0.074 mol) of n-propyl chloride and 0.03 g of aluminum chloride were mixed at room temperature. Vigorous formation of bubbles occurred and the mixture turned yellow and remained homogeneous after the aluminum chloride had dissolved. After 30 minutes the mixture had set into a solid foam. This was triturated with methanol and methylene chloride, a suspension of a hard, granular product was obtained, which was separated off by filtration. This product was then dried. This compound was also a cross-linked, polymeric compound with a melting point greater than 3500 C.



   Example 15
For comparison purposes, n-hexyl chloride was used to join DMA molecules in this experiment to produce the bis product. A mixture of 2.00 g (0.0122 mol) of DMA and 2.94 g (0.0244 mol) of n-hexyl chloride was stirred at room temperature, and 0.1 g of powdered aluminum chloride was added to this mixture. A dark-brown clatalyst complex phase separated immediately. No Bis compound or higher molecular weight products were formed. This shows that C3 or C4 alkyl halides must be used to carry out the process according to the invention and that the reaction with higher alkyl halides does not proceed.



   Substantially the same results are obtained if G3 or C alkyl bromides are used instead of the corresponding chlorides and aluminum bromide instead of aluminum chloride. In the same way, the rings of alkyl adamantane hydrocarbons other than those mentioned here are linked to form bis compounds or polymeric products, or both.



   The bis-products prepared by the process of the present invention are useful as intermediates for the preparation of monomers. Various new polymers can be made from these new monomers. The dihalogen bis compounds can be reacted with formic acid or CO in the presence of strong sulfuric acid according to the Koch reaction (Koch et al., Liebing's Ann. Chem., 618, 251-266, 1958), and the diacids are obtained by substitution a carboxyl group in place of each halogen atom. So z. B. one can convert 1,4-bis (3-chloro-5,7-dimethyl-1 adamantyl) butane into 1,4-bis (3-carboxy-5,7-dimethyl-1 damantyl) butane . Such diacids represent new monomeric compounds from which new polymeric compounds, such as. B.

  Polyesters or polyamides, can be produced. In the same way, the Dihfalogen-Bis compounds can be converted into diols by alkaline hydrolysis, or into diamides by the Ritter reaction. The monomeric compounds obtained in this way can be used for the preparation of polymeric compounds having adamantane rings.



   The monohalogen or hydrocarbon bis-products prepared according to the invention can be fed back into the process for further conversion in order to increase the yield of the dihalogen bis-compounds.

 

Claims (1)

PATENT CLAIM Process for linking adamantane rings by Q- or C4-polymethylene chains, characterized in that a) a solution of 1. a Clo-c9o-Adamlantlan- hydrocarbon consisting of adamantane or an alkyladamantane with at least one unsubstituted bridgehead C- Atom, where the alkyl adamantane has no tertiary alkyl group as a substituent, and 2. produces from a C3-C4 alkyl chloride or bromide, in which the molecular ratio of alkyl halide to adamantane hydrocarbon is more than 1: 1 but less than 2: : 1 when the alkyl halide is tertiary butyl halide, and where the alkyl halide is a primary or secondary alkyl halide when the hydrocarbon is adamantane. b) Dissolve A1C13 or A'lBr3 in this solution at -200 C to + 500 C and stir until the main part of the adamantane hydrocarbon has reacted, the reaction temperature being higher than 100 C if the alkyl halide is tertiary butyl halide, and c) the product is isolated from the reaction mixture, in which 2 adamantane rings are linked between bridge headings by a C3-C4 polymethylene chain. SUBCLAIMS 1. The method according to claim, characterized in that the molar ratio of the alkyl halide to the adamantane hydrocarbon is 1: 1 to 3: 1 and that the end product has 2 Adamantan'ringe and corresponds to the following formula: XA (CH, AX where A is Is adamantane ring with 0-3 alkyl substituents, X is a bridgehead radical consisting of chlorine, bromine, alkyl or hydrogen and n is 3 or 4. 2. The method according to dependent claim 1, characterized in that A 1-2 bridgehead alkyl substituents, consisting of methyl or ethyl, and X is chlorine or bromine. 3. The method according to claim, characterized in that the alkyl halide is a C3 halogen, id, the adtamantane hydrocarbon is 1,3-dimethyladamantane or l-sithyl-3-methyl-adamantane, and 1,3,3-bis (3-halo -5,7-dimethyl-l-adamantyl) propane or 1,3-bis (3-halo-5-ethyl-7-methyl- 1 adamantyl) propane. 4. The method according to claim and dependent claim 2, characterized in that the alkyl halide is a C4 halide, the adamantane hydrogen is 1,3-dimethyladamantane or 1-ethyl-3-methyladamantane and one 1,4-bis (3-halo-5,7-dimethyl- 1-adamantyl) butane or 1,4-bis (3-halo-5-ethyl-7-methyl 1-adamantyl) butane. 5. The method according to claim, characterized in that the alkyl halide is a primary or secondary alkyl halide and the adamantane hydrocarbon has at least 2 unsubstituted bridgehead positions, the molar ratio of the alkyl halide to the adamantane hydrocarbon exceeds 3: 1 and the end product is a polymeric compound with more than 2 adamantane rings which are connected to one another by C3 or C4 polymethylene chains. 6. The method according to dependent claim 5, characterized in that the alkyl halide is an alkyl chloride and the aluminum halide is AlCl3. 7. The method according to dependent claims 5 and 6, characterized in that the adamantane hydrocarbon is 1,3-dimethyladamantane or 1-ethyl-3-methyladamantane and the temperature is more than 150C.