DE2452410C3 - Process for the production of bridgehead n-alkylated or cycloalkylated adamantane hydrocarbons - Google Patents

Description

The invention relates to a process for the production of bridgehead n-alkylated or Cycloalkylated adamantane hydrocarbons by reaction of adamantane or 1,3-dimethyladamantane with 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or cyclooctene.

For the production of alkyüerten in bridgehead position Theoretically, the following different processes are conceivable for adamantane hydrocarbons:

1. a substitution reaction in which the direct adamantyl cation formed electrophilic attack on adamantane reacts with an anion and connects with it,

2. a substitution reaction in which an atom or a group of atoms between a chain carrier or a chain transfer agent and Adamantyl radicals produced by direct radical attack will,

3. a substitution reaction by direct introduction of divalent reactive intermediates such as carbene and nitrene and

4. a ring formation by condensation between suitable components with substituent groups.

Known examples of process (1) are the bromination by means of Br ₂ , only substitution in the bridgehead position being obtained, and the production of a carboxylic acid by means of formic acid. Known examples of process (2) are chlorination and alcohol synthesis by autoxidation. Known processes for alkylating an adamantane compound with an olefin are also (i) the reaction of 1-adamantyl bromide with an olefin in the presence of Lewis acids and (ii) the reaction of adamantanol with an olefin in the presence of Lewis acids. However, these last-mentioned reactions of the Friedet-Crafts type have various disadvantages; For example, large amounts of Lewis acids must be used to catalyze the reaction, it is impossible to subsequently prepare compounds with a long-chain alkyl group, undesired isomerization of the alkyl groups occurs, and attempts to improve the reaction yield lead to the introduction of alkyl groups in more than one position. Further processes for the production of alkylated adamantane hydrocarbons and other alkylated adamantane derivatives are, for example, from the German Offenlegungsschrift 1668662 and from "Chemical Abstracts", Volume 70 (1969), Ref. 77427 x, and ibid., Volume 72 (197Gj, Ref On the other hand, the radical alkylation of saturated hydrocarbons by monolefins in the presence of radical formers, especially peroxides, has been known for a long time (see "Methods of Organic Chemistry", 4th edition, Volume V / la, page 400) It has now been shown, however, that these known processes cannot be applied to the production of n-alkylated or cyclooctylated adamantane hydrocarbons, because considerable amounts of higher substitution products are formed, so that the yield of the desired bridgehead alkylated Adamantane hydrocarbons is low and instead of the n-alkylated branched alkylated adamantanes arises en, even if 1-alkanes are used as the alkylating agent.

The object of the invention is therefore to provide an improved Process for the production of bridgehead n-alkylated or cycloalkylated adamantane hydrocarbons indicate in which this undesirable formation of higher substitution products and formation of branched alkylated adamantanes does not occur and that the desired n-alkyl adamantanes delivers in better yield than the previously known processes.

This object can be achieved by in the presence of hydrogen peroxide, potassium persulfate, Ammonium persulfate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, cumone hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, 2,2'-azo-bis-isobutyl nitrile, 2,2'-azo-bis-propionitrile, diazoaminobenzene, a nitrosoacylallylamine, azothioether or p-nitrobenzene diazonium works as a free radical initiator.

According to the method according to the invention described above, it is possible to be in the bridgehead position n-alkylated or cyclooctylated adamantane hydrocarbons produce in surprisingly high yield without the risk of formation consists of higher substitution products or the formation of branched alkylated products.

Particularly advantageous results are obtained when di-t-butyl peroxide is used as the initiator which provides free radicals is used.

The conditions for the alkylation of adamantane or 1,3-dimethyladamantane, e.g. B. the The reaction temperature and the reaction time depend on the type of free radicals used Initiators, the amounts in which they are used and other factors. For example, if Benzoyl peroxide is used as the free radical initiator, the reaction will normally carried out at 60 to 90 ° C within 2 to 3 hours, while when using dit-butyl peroxide the implementation preferably at 110

carried out up to 150 ° C within 1 to 5 hours will.

The course of the radical alkylation according to the invention of adamantane or 1,3-dimethyladamantane in the bridgehead position shows that the rate of release of hydrogen in the case of adamantane or 1,3-dimethyladamantane compared to the rate of release of hydrogen from C-H bonds in other compounds is large and that the selectivity of the hydrogen release in the positions 1 and 2 largely depends on the steric conformation of the attacking radicals, since has shown that bulky radicals show a more selective withdrawal of hydrogen in the 1-position. In addition, the transfer of the adamantyl radical from the 1-position to the 2-position is negligible small amount. Only 1-1 adducts are obtained.

The invention is illustrated in more detail by the following example.

example

A mixture of 16.435 g (0.1 mol) 1,3-dimethyladamantane, 0.730 g (5 millimoles) di-t-butyl peroxide was obtained and the respective olefin in a 100 ml flask. The mixture then became Heated to 150 ° C for 5 hours while stirring. The reaction products were gas chromatographed analyzed to obtain the results shown in the following table.

Tabel

1-1-

Adduct

(R)

used
Olefin

Molar ratio ^a )

yield
to 1-1 adduct ^b )

yield
an Olefindiraerem ^b )

1-witches 1 9

10 20

1-octene 5 15

• 10 17

-C ₈ H ,, cyclooctene 5 15

n> 10 26

~ ^C 8 ^H 17

^a ) Dimethyladamantane / olefin

^b ) The yields given are based on the converted olefins

I) The alkyl adamantanes thus obtained can be used as Intermediates are used for organic syntheses, for example 1-n-hexyl or 1-n-octyl-adamantane for the synthesis of a carboxylic acid, which is suitable as an oil additive, and its alkali,

- '<> calcium or magnesium salts are used, which is suitable as an anti-rust agent. In addition, the n-alkyl adamantanes can lead to the corresponding adamantols are oxidized. The esterification of these adamantols with phosphoric acid or sulfur

Ester compounds obtained from acidic acid can be used as hydraulic oils. Furthermore, this can n-Alkyladamantane itself can be used as a lubricant, and n-Alkyladamantane derivatives can be used as Insecticides and used as anti-flu medicines

Hi.

Claims (2)

Patent claims: 1. Procedure for setting up in bridgehead position n-alkylated or cycloalkylated Adamantane hydrocarbons by reaction of adamantane or 1,3-dimethyladamantane with 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or cyclooctene, characterized in that in the presence of hydrogen peroxide, Potash persulfate, ammonium persulfate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, 2,2'-azo-bis-isobutyl nitrile, 2,2'-azo-bis-propionitrile, diazoaminobenzene, a nitrosoacylallylamine, azothioether or p-nitrobenzene diazonium as free radical initiator works. 2. The method according to claim 1, characterized in that the alkylation is carried out in the presence of di-t-butyl peroxide within 1 to 5 hours at a temperature of 110 to 150 ° C.