EP2285764A2 - Monoetherified diols of diamondoids - Google Patents

Abstract

The invention relates to functionalised diols of diamondoids wherein one of the two hydroxy groups is masked by a protective group, and to methods for producing said functionalised diols. The protective group is a -CHR¹R² group, wherein R¹ and R² are alkyl groups. The protective group contains at least one halogen atom. The monoethers of the diamondoid diols are produced by reacting the diamondoid diol with a halogenated alcohol CHOHR¹R² in the presence of a catalyst acid. The monoetherified diols enable the targeted production of derivatives of the diamondoids, for example the corresponding amino alcohols and aminocarboxylic acids. To this end, the diamondoid monoether is reacted with a halogenonitrile in a Ritter reaction, in a first step, to form the corresponding monoether amide. The corresponding amino alcohol is produced from said monoether amide by reacting the protective group -CHR¹R² first with trifluoroacetic acid to form the alkanoyloxy group, and then obtaining the amino alcohol by reaction with thiourea, ethanol and glacial acetic acid. The amino alcohol can be reacted with sulphuric acid / formic acid or fuming sulphuric acid / formic acid to form the corresponding amino carboxylic acid. The amino, hydroxy, and carboxyl groups of the diamondoids can be converted into a plurality of other functional groups.

Description

 Patent application

Mono-etherified diols of the diamondoids

The present invention describes functionalized diols of the diamondoids in which one of the two hydroxy groups is masked by a protecting group, as well as methods for the preparation of these functionalized diols. The protecting group is a group -CHR ¹ R ² where R ^{1 is} an alkyl group and R ^{2 is} hydrogen or an alkyl group. The protecting group contains at least one halogen atom, preferably fluorine. The monoetheretherated diols allow the targeted production of derivatives of the diamondoids, for example the corresponding amino alcohols and aminocarboxylic acids.

Description and introduction of the general field of the invention

The present invention relates to functionalized diamondoids. These are monoetheretherated diols of the diamondoids, which may optionally have, in addition to the ether and the hydroxy group, further covalently bonded functional groups.

State of the art

Diamondoids are cage-like substituted and unsubstituted adamantane series compounds. The adamantane series includes adamantane, diamantane, triamane, tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nomen- namane, decamantane, undecamantane and similar compounds as well as all isomers and stereoisomers.

These compounds have a diamondoid topology, i. The arrangement of their carbon atoms can be aligned with a fragment of a FCC diamond lattice.

The prior art distinguishes lower and higher diamondoids.

Adamantane, diamantane and triamantane and all substituted or unsubstituted derivatives of these compounds are understood as "lower diamondoids." These lower diamondoids do not appear in different isomeric forms, nor are they chiral, thus distinguishing them from higher diamondoids.

The term "higher diamondoids" refers to all substituted and unsubstituted tetramantanes, pentamantanes, hexamantanes, heptamantanes, octamantanes, nonamantanes, decamantanes, undecamantanes, etc., and their isomers and stereoisomers.

Adamantane is the smallest member of the Diamantoid series and consists of a single cage structure of the diamond crystal lattice. Diamantan consists of two Adamantane subunits condensed over the faces, triamantane of three, tetramantane of four, etc. While there is only one isomeric form of adamantane, diamantane, and triamantane, there are already four isomers of tetramantane, two of which form an enantiomeric pair. ie, four different possible arrangements of the adamantane subunits. The number of possible isomers increases nonlinearly with each higher member of the diamondoid series.

From five adamantane subunits, i. from pentamantane, structures with different molecular formulas exist for a given number of adamantane subunits. These different molecular formulas result from special arrangements of the adamantane subunits.

The four different structures of the tetramantane are isotetramantanes [1 (2) 3], anti-tetramantanes [121] and the two enantiomeric skew tetramantanes [123]. All four tetramantanes have the molecular formula C22H28 (molecular weight 292).

The naming of these diamondoids is carried out according to a convention described by Balaban et al. in "Systematic Classification and Nomenclature of Diamond Hydrocarbons-I", Tetrahedron, 1978, 34, 3599-3609.

There are ten different pentamantanes, of which nine have the molecular formula C ₂₆ H ₃₂ (molecular weight 344). Among these nine pentamantanes, there are three pairs of enantiomers generally depicted as [12 (1) 3)], [1234] and [1213], with the remaining three pentamantanes containing [12 (3) 4], [1212] and [1 (2,3) 4]. Furthermore, there is a pentamantane [1231] with the molecular formula C25H30 (molecular weight 330).

Hexamantanes can be present in thirty-nine possible structures, of which twenty-eight have the molecular formula C ₃₀ H ₃₆ (molecular weight 396). Ten hexamantanes have the molecular formula C ₂ gH ₃₄ (molecular weight 382), and the remaining hexamantane [13212] has the molecular formula C ₂₆ H ₃₀ (molecular weight 342). It is postulated that heptamantanes can be present in 160 possible structures, of which 85 have the molecular formula C ₃₄ H ₄₀ (molecular weight 448) and of which seven are achiral. Of the remaining heptamantanes, 67 have the sum formal C ₃₃ H ₃₈ (molecular weight 434), six have the sum formula C ₃₂ H ₃₆ (molecular weight 420), and the remaining two have the empirical formula C ₃₀ H ₃₄ (molecular weight 394).

Octamantanes have eight adamantane subunits and exist in structures with five different molecular weights. Of the octamantanes, 18 have the molecular formula C ₄₃ H ₃₈ (molecular weight 446). Octamantanes also have the empirical formulas C ₃₈ H ₄₄ (molecular weight 500), C ₃₇ H ₄₂ (molecular weight 486), C ₃₆ H ₄₀ (molecular weight 472) and C ₃₃ H ₃₆ (molecular weight 432).

The nonamantanes have six families with different molecular weights and the following structural formulas: C ₄₂ H ₄₈ (molecular weight 552), C ₄ -IH ₄₆ (molecular weight 538), C ₄₀ H ₄₄ (molecular weight 498), C ₃₇ H ₄₀ (molecular weight 484 ) and C ₃₄ H ₃₆ (molecular weight 444).

The decamantans have seven families with different molecular weights. Among the decamantanes there is a single compound with the molecular formula C ₃₅ H ₃₆ (molecular weight 456) which is structurally compact compared to the other decamantanes. The other families of decamantane have the following molecular formulas: C ₄₆ H ₅₂ (molecular weight 604), C ₄₅ H ₅₀ (molecular weight 590), C ₄₄ H ₄₈ (molecular weight 576), C ₄₂ H ₄₆ (molecular weight 550), C ₄₁ H ₄₄ (Molecular weight 536) and C ₃₈ H ₄₀ (molecular weight 496).

Undecamantans have families of eight different molecular weights. Among the undecanantanes there are two compounds with the sum formal C ₃₉ H ₄₀ (molecular weight 508), which are structurally compact compared to the other undecamantanes. The other undecamantane families have the following molecular formulas: C ₄ - | H ₄₂ (molecular weight 534), C ₄₂ H ₄₄ (molecular weight 548), C ₄₅ H ₄₈ (molecular weight 588), C ₄₆ H ₅₀ (molecular weight 602), C ₄₈ H ₅₂ (molecular weight 628), C ₄₉ H ₅₄ (molecular weight 642) and C ₅₀ H ₅₆ (molecular weight 656).

In nature, diamondoids are found in petroleum, natural gas and other materials rich in hydrocarbon compounds. Among the naturally occurring diamondoids are also alkyl-substituted compounds.

Diamantoids are of interest as starting materials for microelectronics, pharmacy, nanotechnology and materials science. Potential applications of diamondoids and their derivatives include, for example, the production of temperature-stable plastics, coatings with tailored conductivities for LEDs and transistors, nanoelectronics, and their use in pharmaceuticals against viral and neurodegenerative diseases.

Of particular interest here are diamantanes having hydroxyl, carbonyl, carboxyl, amino and / or aminocarbonyl groups, since they are important intermediates for the preparation of oligomeric and polymeric diamantanes. In addition, the abovementioned functional groups can be substituted by other functional groups, so that substituted diamantanes in this way represent important starting materials for the preparation of further substituted diamantanes.

It is known to those skilled in the art that there are different carbon atoms in the backbone of the diamondoids: secondary (2 ° or C-2), tertiary (3 ° or C-3) and quaternary (4 ° or C-4) carbon atoms, with quaternary Carbon atoms from Th-amantan occur. Quaternary carbon atoms can not undergo substitution reactions. Chemical reactions can only occur on secondary and tertiary carbon atoms of the diamondoids. It should be noted that some of the tertiary and secondary carbon atoms, respectively, are equivalent. Derivatives substituted on these equivalent secondary or tertiary carbon atoms are identical.

There are three reaction mechanisms for the derivatization of the diamondoids: nucleophilic (S _N 1 -type) and electrophilic (S _E 2 -type) substitution reactions and free radical reactions. These are described, for example, in EP 1 453 777 B1.

There are already some papers on the introduction of different functional groups in diamondoids, for example:

1. L. Vodicka, J. Janku, J. Burkhard: "Synthesis of diamantanecarboxylic acids with the carboxyl groups at tertiary carbon atoms." Collect Czech Chem Commun 1983, 48, 1162-1172

2. L Vodicka, J Burkhard, J Janku: "Preparation of diamantanecarboxylix ac-ids with carboxyl groups on one secondary and one tertiary carbon atom".

Collect Czech Chem. Commun. 1986, 51, 867-871

3. J Burkard, J Janku, P. Zachar, L. Vodicka: "Hydroxydiamantanecarboxylic and diamantanecarboxylic acids". Sb Vys Sk Chem Techn 1989, D57, 5-16

4. J Burkard, J Janku, L Vodicka: "Diamond Anecarboxylic Acids with Carboxylic on Tertiary Carbon Atoms of the Diamond- skelene Skeleton" Sb Vys Sk Chem

Techn 1983, D47, 73-99

5. J Janku, J Burkard, L Vodicka: "Preparation and isomethication of hydroxy- diamondant carboxylic acids". Sb Vys Sk Chem Techn 1984, D49, 25-38

6. L Vodicka, SD Isaev, J Burkhard, J Janku: "Synthesis and reactions of hydroxydiamantanones". Collect Chem Czech Commun 1984, 49, 1900-1906

The methods described here produce product mixtures.

M Padmanaban, S Chakrapani, G Lin, T Kudo, D Parthasarathy, C Anyadiegwu, C Antonio, R Dammel, S Liu, F Lam, T Maehara, F Iwasaki, M Yamaguchi: "Novel Diamantane Polymer Platform for Resist Applications ", J Photopol Sei Technol 2007, 20, 719-728 describes the preparation of methacrylic acid derivatives of diamantane. The synthesis of 3-alkyl-3-diamantyl methacrylates is carried out by first diamantane is reacted with concentrated sulfuric acid to 3-diamanderone. Subsequently, 3-diamantone is reacted with an alkylgrignard compound and then with methacryloyl chloride. In this reaction sequence, it is not possible to introduce substituents on different carbon atoms of the diamond backbone and the yield of the respective methacrylic acid derivative is only 40%. Furthermore, this work describes the preparation of 9-hydroxy-4-diamantyl methacrylate. For this purpose, Amantan reacted with chlorosulfuric acid and sulfuric acid to 4,9-Diamantandiol. Then, equimolar amounts of diol and methacryloyl chloride react to give the 9-hydroxy-4-diamantyl methacrylate. However, the yield is only 5%.

WO 00/342141 A1 describes aminohydroxyadamantane derivatives and their use as dipeptidyl peptidase IV inhibitors, for example for the treatment of diabetes. However, the methods presented for the preparation of these adamantane deities do not permit, in the case of two identical functional groups, only one of them to be converted into another functional group.

WO 2007/069656 A1 describes a process for preparing a polymerizable hydroxydiamantyl ester compound. In this case, a 4,9-Diamantandiol prepared by dihalogenation and subsequent hydrolysis with water. Subsequently, the 4,9-diamondediol is esterified with a mixture of an unsaturated carboxylic acid and an anhydride of an unsaturated carboxylic acid in the presence of a polymerization inhibitor and an acidic catalyst

In WO 2006/010362 A1 and in L Wanka, C Cabrele, M Vanejews, PR Schreiner: "γ-Aminoadamantanecarboxylic acids through direct CH bond amidations". Eur J Org Chem 2007, 1474-1490, Aminoadamantancarbonsäuren are described. These compounds are prepared by direct amidation using a Ritter reaction in nitrating acid. A prior halogenation of the Adamantans is not necessary. The Ritter reaction is known to the skilled person. It allows the conversion of alkenes, secondary or tertiary alcohols with nitriles to amides. If halogen niches are used, a haloalkanoyl group is introduced, which is then split off again by reaction with thiourea. In this way, for example, tertiary alcohols can be converted into the corresponding tertiary amino compounds, see A Jirgensons, V Kauss, I KaIvinsh, MR Gold: "A Practical Synthesis of tert-Alkylamines via the Ritter Reaction with Chloroacetonitriles." Synthesis 2000, 12, 1709-1712. US 2002/0177743 A1 describes derivatives of higher diamondoids which have one or two polymerisable functional groups, as well as intermediates which are useful for the synthesis of the polymerizable higher diamondoids. Both the intermediates and the polymerizable higher diamondoids include, for example, derivatives having hydroxyl, amino and carbonyl functions. Also, production methods for substituted higher diamondoids are proposed. However, all of the processes proposed in US 2002/0177743 A1 use educt mixtures, so that product mixtures are formed. The processes proposed in this document would also yield product mixtures when using pure starting materials, and it is not possible to introduce certain functional groups in a regio- and / or stereoselective manner.

Likewise, EP 1 453 777 B1 describes similar functionalized higher diamond oxides as described in US 2002/0177743 A1. EP 1 453 777 B1 states that diamondoids react in nucleophilic substitutions to S _N 1, resulting in stable diamondoid carbocations. Such stable diamondoid carbocations can be generated, for example, from hydroxylated diamondoids. Fokina, BA Tkachenko, A. Merz, M. Seafin, JEP Dahl, RMK Carlson, A. Fokin, PR Schreiner: "Hydroxy derivatives of diamantanes, triamantanes, and [121] tetramantanes:""DE 10 2005 058 357 A1" selective preparation of bis-apical derivatives. " Eur J Org Chem 2007, 4738-4745 describes how diamondoids react to the corresponding nitroxylated derivatives. The nitroxy groups can then be converted into hydroxy groups.

It is known to the person skilled in the art that the introduction of hydroxy groups is advantageous because the hydroxy group can be converted into a multiplicity of further functional groups, for example into amino and carbonyl groups. However, not a single of the publications mentioned here discloses a process with which it would be possible to specifically convert only a single one of several hydroxyl groups into another functional group and thus to prevent the formation of product mixtures or at least the number of possible different reaction products of to reduce polyhydroxylated diamondoids. In many applications, for example in microelectronics, materials science and pharmacy, it is desirable or even mandatory that they are pure substances rather than substance mixtures and that the substances are halogen-free. However, the separation of mixtures of substances is often very complicated and expensive. Furthermore, many previously known processes for preparing substituted diamondoids require the halogenation of the diamondoid skeleton. The halogenation is usually a bromination. Therefore, production methods are desirable in which the smallest possible number of different products is produced and the least possible without bromination (or generally without halogenation). Preferred are those processes in which only a single substance is produced as the main product.

In contrast, the present invention for the first time provides derivatives of diamondoids which have two hydroxy groups, one of which is masked by a protective group. The derivatives of the diamondoids according to the invention therefore permit the selective conversion of one hydroxy group into another functional group, with the second, masked hydroxy group subsequently being released again and optionally subsequently being converted into another functional group as well.

task

The object of the present invention is to provide functionalized diols of the diamondoids in which one of the two hydroxyl groups is masked by a protective group, and to provide processes for their preparation.

Solution of the task

This object of providing functionalized diols of the diamondoids, in which one of the two hydroxyl groups is masked by a protective group, is achieved according to the invention by compounds of the formula (I)

where D is a diamondoid,

R ^{1 is} a linear or branched alkyl group -C _n H _p X _q ,

^Where n is a natural number from 1 to 25,

^■ p is an integer between O and 50 and q is a natural number between 1 and 51, ■ and the sum of q and p (2n + 1) gives,

R ^{2 is} hydrogen or a linear or branched alkyl group -C _m H ₁ -X ₃ ,

^Where m is a natural number from 1 to 25,

^■ r and s are integers between 0 and 51, ■ and the sum of r and s (2m + 1) gives,

X is a halogen selected from fluorine, chlorine or bromine,

R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another represent hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, a heteroaryl group having 5 to 18 ring atoms, of which 1 or 2

Atoms are heteroatoms selected from nitrogen, oxygen,

Sulfur, and the remaining ring atoms are carbon atoms.

Surprisingly, it has been found that groups according to formula (II)

as protective groups for the masking of hydroxy groups. Here, R ¹ and R ² are defined as described above.

The functionalized diols of the diamondoids according to the invention are explained below, the invention encompassing all the preferred embodiments listed below individually and in combination with one another.

In the functionalized diols of the diamondoids according to the invention, one of the two hydroxy groups is masked by a protective group of the formula (II), in the form of an ether. Functionalized diols of diantides according to formula (I) according to the invention are therefore also referred to below as "diamondoid monotherms" or in short as "monoethers".

The term "diamondoid" refers to the substituted and unsubstituted caged compounds of the adamantane series described at the beginning, ie it comprises, for example, but not exhaustively substituted and unsubstituted adamantane, diamantane, theamantane, tetramantane, pentamantane, hexamantane, heptamantane, Octamantane, nonamantane, decamantane, undecamantane, etc. Substituted diamondoids carry substituents R ³ , R ⁴ , R ⁵ and R ⁶ according to formula (I). "Diamondoid" or "diamondoids" further includes homologous, analogous and isomeric compounds.

"Homologous" diamondoids are understood to mean a series of compounds which can be represented by a general empirical formula and in which a compound of this series from the previous substance is formed by "adding" another "chain member." In the case of homologous diamondoids the chain link is formally a C ₄ H ₄ unit: formally adamantane is obtained by adding a C ₄ H ₄ unit diamantane, then by adding a C ₄ H ₄ unit thamantane, etc.

"Analogous" diamondoids, on the other hand, are compounds with the same number of adamantane subunits, but different molecular formulas and different molecular weights Analogs, as described above, exist for diamondoids containing at least five adamantane subunits, ie, from pentamantane.

"Isomeric" diamondoids in the sense of the present invention have the same empirical formula but a different arrangement of the adamantane subunits and / or the substituents R ³ , R ⁴ , R ⁵ and R ⁶ .

"Lower diamondoids" are understood to mean all substituted and / or unsubstituted adamantanes, diamantanes and triamantanes and their derivatives and isomers Substituted and / or unsubstituted tetramantanes, pentamantanes, hexamantanes, heptamantanes, octamantanes, nonamantanes, decamantanes, undecamantanes (elev Adamantane subunits) and all other diamondoids containing more than eleven adamantane subunits and their derivatives, analogs and isomers are referred to as "higher diamondoids".

As described above, there are only one isomeric form of unsubstituted adamantane, diamantane and thamantane, but already four isomers of the unsubstituted tetramantane, two of which form an enantiomer pair, ie four different possible arrangements of the adamantane subunits. If the lower diamondoids adamantane, diamantane and triamantane are substituted, they also occur in different isomers, provided that at least one of the four substituents R ³ , R ⁴ , R ⁵ and R ⁶ according to the above definition is not hydrogen. From tetramantane different isomers are possible both in the respective unsubstituted and in the substituted diamondoid.

The present invention relates to all lower, higher, substituted, unsubstituted, homologous, analogous and / or isomeric diamondoids according to the above definitions.

According to the above definition, substituents R ³ , R ⁴ , R ⁵ and R ^{6 are} bonded to the functionalized diols of the diamondoids according to the invention. These substituents are, as defined above, independently of one another hydrogen, a linear or branched alkyl group, a cyclic alkyl group, an aryl or a heteroaryl group.

When R ³ , R ⁴ , R ⁵ and / or R ⁶ is a linear or branched alkyl group, each of these alkyl groups independently contains 1 to 20 carbon atoms. These alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, 1-butyl, 2-butyl, tert-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 3-methylbutyl, 2,2-dimethylpropyl, and all isomers of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl.

If R ³ , R ⁴ , R ⁵ and / or R ⁶ are a cyclic alkyl group having 3 to 20 carbon atoms, this is preferably selected from cyclopentyl, cyclohexyl, cycloheptyl.

When R ³ , R ⁴ , R ⁵ and / or R ⁶ is an aryl group having 6 to 18 carbon atoms, it is selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, tetracenyl.

R ³ , R ⁴ , R ⁵ and / or R ⁶ may further be a heteroaryl group having from 5 to 18 ring atoms, of which 1 or 2 atoms are heteroatoms selected from nitrogen, oxygen and sulfur, which include the remaining ring atoms are carbon atoms. The heteroaryl group is selected from furanyl, benzofuranyl, isobenzofuranyl, pyrrolyl, indolyl, isoindolyl, thiophenyl, benzothiophenyl, benzo [c] thiophenyl, imidazolyl, benzimidazolyl, pyrazolyl, indazolyl, oxazolyl, benzoxycolyl, isoxazolyl, benzisoxazolyl, thiazolyl, benzothiazolyl, pyridinyl , Quinolinyl, isoquinolinyl, pyrazinyl, quinoxalinyl, acridinyl, pyrimidinyl, quinazolinyl, pyridazinyl, cinnolinyl.

R ¹ is a linear or branched alkyl group -C _n H _p X _q . Where n is a natural number from 1 to 25, p is an integer between 0 and 50, and q is a natural number between 1 and 51. The sum of p and q is (2n + 1).

R ² is hydrogen or a linear or branched alkyl group -C _m H ₁ -X ₃ . Where m is a natural number from 1 to 25, and r and s are integers between 0 and 51. The sum of r and s is (2m + 1).

The halogen atom X in R ¹ and R ² is selected from fluorine, chlorine and bromine. Thus, R ^{1 is} formally an alkyl group -C _n H _{2n +} I, in which at least one and at most all hydrogen atoms are replaced by a halogen atom X. R ² is an alkyl group -C _m H ₂ m ₊ i, in which no one to all hydrogen atoms are replaced by a halogen atom X, unless R ^{2 is} a hydrogen atom.

If R ¹ or R ^{2 are} at least monohydrogenated and perhalogenated alkyl groups -C _n H _{2n + I} or -C _m H _{2m + 1} , these are, for example, halogenated methyl groups as defined above. , Ethyl, n-propyl, isopropyl, 1-butyl, 2-butyl, tert-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 3-methylbutyl, 2, 2-dimethylpropyl groups and to all isomers of the above definition halogenated hexyl, heptyl, octyl, nonyl, decyl, decode, and dodecyl groups. Analogously, R ^{2 may} also be the corresponding non-halogenated alkyl groups.

The sum of n and m is a natural number between 1 and 25. According to the definitions of R ¹ , R ² , m, n, p, q, r and s given here, the protective group -CHR ¹ R ² according to the invention therefore contains at least two and a maximum of 26 carbon atoms. Of course, R ¹ or R ² can only be branched if n or m is at least equal to 3.

In a preferred embodiment, the halogen atom X is fluorine.

In a further preferred embodiment, the radicals R ³ and R ⁴ each represent a hydrogen atom and the radicals R ⁵ and R ⁶ each represent a linear or branched alkyl group having 1 to 20 carbon atoms.

Furthermore, those embodiments are preferred in which R ³ and R ^{4 are} hydrogen and R ⁵ and R ^{6 are} identical. Very particular preference is given to those functionalized diols in which R ³ and R ^{4 are} hydrogen, R ⁵ and R ^{6 are} identical and R ⁵ and R ^{6 are} a linear or branched alkyl group having 1 to 20 carbon atoms.

In a further preferred embodiment, the functionalized diols of the diamondoids according to the invention are compounds in which the protective group of the formula (II)

contains a total of 2 to 12 carbon atoms.

In a further preferred embodiment, the protecting group of the formula (II) contains a total of 2 to 12 carbon atoms, and the halogen atom X is fluorine.

Most preferred are protecting groups -CHR ¹ R ² selected from -O-CH ₂ -CF ₃ , -O-CH ₂ -CF ₂ H, -O-CH ₂ -CF ₂ -CF ₃ , -O-CH ₂ - CF ₂ -CF ₂ H, -O-CH- (CF ₃ ) ₂ , -O-CH ₂ - (CF ₂ ) ₂ -CF ₃ , -O-CH ₂ - (CF ₂ ) ₂ -CF ₂ H, - O-CH ₂ - (CF ₂ ) ₃ -CF ₃ , -O-CH ₂ - (CF ₂ ) ₃ -CF ₂ H. The functionalized diols of the diamondoids according to the invention are prepared by reacting a diamondoid diol (III) with a halogenated alcohol (IV) in the presence of a Bronsted or Lewis acid catalyst according to

responding. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} as defined above.

The reaction of diamondoid diol (III) and alcohol (IV) to the monoether (I) according to the above equation is an S _N 1 reaction.

The process according to the invention for the preparation of the functionalized diols of the diamondoids comprises the following steps: a) mixing a diamondoid diol DR ³ R ⁴ R ⁵ R ⁶ (OH) ₂ with a halogenated alcohol CHOHR ¹ R ² , where D, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} as defined above, b) adding a catalyst acid, c) stirring at -20 ° C to 100 ° C, d) terminating the reaction by adding an amine or water, e ) Isolating the crude end product, f) purifying the crude end product.

The mixing ratio of diamondoid diol and halogenated alcohol plays no role in the success of the reaction, ie for the successful formation of the monoether according to the invention. Accordingly, the mixture of diamondoid diol and halogenated alcohol may be concentrated or dilute solutions or suspensions. Fluorinated alcohols are preferably used, for example HO-CH ₂ -CF ₃ , HO-CH ₂ -CF ₂ H, HO-CH ₂ -CF ₂ -CF ₃ , HO-CH ₂ -CF ₂ -CF ₂ H, HO-CH - (CF ₃ ) ₂ , HO-CH ₂ - (CF ₂ ) ₂ -CF ₃ , HO-CH ₂ - (CF ₂ ) ₂ -CF ₂ H, HO-CH ₂ - (CF ₂ ) ₃ -CF ₃ , HO-CH ₂ - (CF ₂ ) _S -CF ₂ H. The use of fluorinated alcohols is particularly advantageous because of their low boiling points compared to the non-fluorinated analogs.

As the catalyst acid, a Bronsted or Lewis acid is selected. Suitable catalyst acids are, for example, CF ₃ SO ₃ H and p-toluenesulfonic acid. It will be advantageous 10 ^{~ 5} vol% to 10% by volume of catalyst acid, preferably about 0.1% by volume, based on the volume of the solution of the diamondoid diol added.

After addition of the catalyst acid, the reaction mixture is stirred at about -20.degree. C. to 100.degree. Preferred is a reaction temperature of 25 ° C to about 40 ° C. Which reaction time should be chosen for a given combination of diamondoid diol and halogenated alcohol, the skilled artisan by routine experimentation and without departing from the scope of the claims easy to determine. Halogenated alcohols are compounds HO-CHR ¹ R ² , which according to the above definition of the protecting group -CHR ¹ R ^2, at least one halogen atom X selected from fluorine, chlorine and bromine. In general, higher diamondoids are more reactive than their lower homologues and analogues in terms of the required reaction time and temperature. Furthermore, OH groups are more reactive in medial positions of the diamondoid than in apical ones.

The etherification reaction between diamondoid diol and halogenated alcohol can be terminated by adding an amine or by adding water. By adding an amine, the catalyst acid is neutralized. Suitable amines are, for example, thethylamine and diisopropylethylamine (DIPEA). When the reaction is terminated by the addition of an amine, the crude end product is advantageously isolated by removal of the solvent.

Alternatively, the reaction can be stopped by adding water. In the case of completion of the reaction by addition of water, the crude end product is isolated by extraction from the reaction mixture, for example with chloroform.

The termination of the reaction by addition of an amine is preferred, since in this case higher yields of the monoether are achieved than when stopping the reaction. action by adding water. At the end of the reaction by addition of water more work steps are also necessary (extraction, removal of the extractant).

The crude end product is purified by methods known to those skilled in the art, for example by column chromatography. Cleaning methods for diamondoid derivatives are known to those skilled in the art and may be used without departing from the scope of the claims.

The monoethers of the diamondoids according to the invention can be used for the specific preparation of further diamondoid derivatives. Particularly advantageous is the Ritter reaction of the free hydroxy group with a halogenated bonsäurenitril to an amide according to

(I) (V)

Here, R ¹ to R ^{6 are} as defined above, R ⁷ is a linear, branched or cyclic alkylene group -C ₁ H ₂ T, wherein t is a natural number of 1 to 1 1, and Y is a halogen atom selected from fluorine , Chlorine, bromine, iodine.

To carry out the Ritter reaction, the monoether (I) is dissolved in glacial acetic acid and the halogenated nitrile is added at room temperature. Subsequently, concentrated sulfuric acid is added. The reaction is stopped by adding water. Suitable nitriles for the Ritter reaction and the required reaction conditions are known to the person skilled in the art and can be used without departing from the scope of the patent claims.

The nitriles are selected, for example, from halogenated acetonitrile, propionitrile, butyronitrile, valeronitrile, capronitrile, heptanoic acid nitrile, octanoic acid nitrile, Nonanoic nitrile, decanoic acid nitrile, undecenonitrile, lauric acid nitrile and cyclopentanecarbonitrile. Preference is given to using chlorinated nitriles. The amides of the monoethers formed in this reaction are referred to below as "monoether amides".

The monoether amides thus formed can be used to prepare amino alcohols or aminocarboxylic acids of the diamondoids.

To prepare amino alcohols, a hydroxy group of a diamantane diol having a protecting group -CHR ¹ R ^{2 is} masked in the first step.

This monoether is reacted as described above in a Ritter reaction to the corresponding monoether amide. Subsequently, the alkoxy group -O-CHR ¹ R ^{2 of} the monoether amide reacts with trifluoroacetic acid. This is exemplified in Example 6 for the preparation of 4-trifluoroacetoxy-9- (2-chloroacetylamino) -diamantane 8 from 2-chloro-Λ / - [9- (2,2,2-thfluoroethoxy) diamantan-4-yl acetamide 5 shown.

Finally, both alkanoyl groups (-OC-CF ₃ and -COR ⁷ Y) are removed by heating with thiourea, ethanol and glacial acetic acid, and then the reaction solution is made alkaline with an aqueous alkali, for example NaOH or KOH. Finally, the crude aminoalcohol is isolated from the reaction mixture and purified. This is exemplified in Example 7 for the preparation of 4-amino-diamantane-9-ol 9 from 4-trifluoroacetoxy-9- (2-chloroacetylamino) -diamantane 8.

From this amino alcohol can be produced the corresponding aminocarboxylic acid. For this purpose, the aminoalcohol is reacted with a mixture of oleum and 100% formic acid at temperatures between -20 ° C and 0 ° C. Then, an alkali is added, for example, NaOH or KOH to precipitate the crude aminocarboxylic acid salt. The aminocarboxylic acid salt is then separated, purified and dried. It is then reacted with thionyl chloride / methanol to give the corresponding aminocarboxylic acid methyl ester. This is then isolated and purified. This is exemplified in Example 10 for the preparation of 4-amino-9-diamantancarbonsäuremethyl- ester 11 from 4-aminodiamantan-9-ol 9. By adding a strong mineral acid and heating, the ester can be saponified to give the carboxylic acid hydrochloride, which is finally separated, purified and dried, as shown in Example 11 for the preparation of 4-amino-9-diamantancarbonsäurehydrochlorid 12 from 4-amino-9-diamantancarbonsäuremethylester 11 ,

Alternatively, aminocarboxylic acids of the diamondoids can be prepared by heating a monoether amide with thiourea, ethanol and glacial acetic acid. Subsequently, the reaction solution is diluted with water and made alkaline with an alkali, for example NaOH or KOH, then the resulting monoether-amine is isolated and purified. This is exemplified in Example 4 for the preparation of 9- (2,2,2-trifluoroethoxy) -diamantane-4-amine 6 from 2-chloro-N- [9- (2,2,2-trifluoroethoxy) -diamantane. 4-yl] -acetamide 5. Subsequently, the monoether-amine is reacted with a mixture of concentrated sulfuric acid and 100% formic acid at temperatures between -20 ° C and 0 ° C. The mixture is then placed on ice and the amino carboxylic acid isolated and purified. This is shown by way of example in Example 5 for the reaction of 9- (2,2,2-trifluoroethoxy) diamantane-4-amine 6 to 4-amino-9-diamantane carboxylic acid 7.

The preparation of aminocarboxylic acids by conversion of the corresponding amino alcohol into the methyl ester and subsequent saponification of the ester with a strong mineral acid (see Examples 10 and 11) is preferred.

Amino alcohols and aminocarboxylic acids of the diamondoids are particularly well suited to selectively introduce other functional groups. This is below for the preparation of nitro alcohols of the diamondoids from the corresponding aminoalcohols.

Thus, from the amino alcohols of the diamondoids, the corresponding nitro alcohols can be prepared, for example by reaction with meta-alcohols. Chloroperbenzoic acid (mCPBA). This is illustrated in Example 8 for the oxidation of 4-aminodiamantan-9-ol) to 4-nitrodiamantane-9-ol 10.

Further possibilities for converting amino, hydroxyl and carboxyl groups into other functional groups are known to the person skilled in the art.

The protective group -CHR ¹ R ² according to the invention can be converted back into an OH group by treatment with a strong acid, for example CF ₃ COOH or H ₂ SO ₄ , and subsequent neutralization with an alkali, for example NaOH or KOH.

With the aid of the monoethers of the diamantides described in the present invention, it is possible, for example, to produce medicinally relevant diamondoids in a targeted manner and in higher yield and purity than hitherto. In addition, the monoethers according to the invention allow the electron exit behavior of the diamondoids to be controlled by targeted introduction of groups which emit good or poor electron. Thus, the monoethers of the invention and the process for their preparation are useful in the production of Diamantoiddehvaten for electronic components. Aminocarboxylic acids and aminoalcohols of the diamondoids also allow the introduction of functional groups for the polycondensation and also for the production of peptides.

embodiments

Embodiment 1: Preparation of 3- (2,2,2-trifluoroethoxy) -adamantan-1-ol

1. 2,2,2-trifluoroethanol, CF ₃ SO ₃ H, Δ

2. triethylamine

0.3 mmol (50 mg) of 1, 3-adamantanediol 1 with a purity of> 99% were dissolved in 40 ml of 2,2,2-trifluoroethanol and treated at 40 ° C in a water bath with 10 ul_ CF ₃ SO ₃ H. After stirring at the same temperature for 2.5 h, the acid was neutralized with 20 μl of triethylamine and the solvent was stripped to dryness. The slightly oily crude product was separated on silica gel with ethyl acetate: hexane 8: 2 as eluent. This gave 56 mg (75%, Rf = 0.44) of the pure mono- ether 2 (slowly crystallizing oil).

Spectroscopic data for 3- (2,2,2-trifluoroethoxy) -adamantan-1-ol:

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 3.80 (2H, q, J = 8.8 Hz), 2.35 (2H, br s), 1.78-1.62

(1 OH, m), 1.59-1.47 (3H, m) 1 ³ C-NMR (100 MHz, CDCl ₃ ) δ: 124.2 (q, J = 277.7 Hz), 76.2, 70.4, 59.4 (q, J =

34.2 Hz), 48.7, 44.0, 39.8, 34.7, 30.9

¹⁹ F NMR (376 MHz, CDCl ₃ ) δ: -74.55

IR data (KBr): 3350.3, 2919.9, 2858.7, 1456.3, 1352.5, 1275.8, 1 171.1, 1 151.7,

1 131.2, 1 1 1 1.4, 1094.5, 1014.2, 963.0 cm ^-1 melting point: 78 ° C

HRMS: calculated for Ci ₂ H ₁₇ F ₃ O ₂ : 250.1 181; found: 250.1 182

C ₁ H ₁ N: calculated for C ₁₂ H ₁₇ F ₃ O ₂ (250.26): C 57.59, H 6.85; found: C 57.43, H

6.83 Embodiment 2:

Preparation of 4- (2,2,2-trifluoroethoxy) diamantan-9-ol

1. 2,2,2-trifluoroethanol, CF ₃ SO ₃ H, Δ

2. triethylamine

2.5 mmol (551 mg) 4,9-Diamantandiol 3 with a purity of> 99% were dissolved in 10O mI 2,2,2-trifluoroethanol and treated at 40 ° C in a water bath with 50 ul_ CF ₃ SO ₃ H. After 4 h stirring at the same temperature, the acid was neutralized with 100 ul_ triethylamine and the solvent evaporated to dryness. The colorless, solid crude product was separated on silica gel with ethyl acetate: hexane 8: 2 as eluent. This gave 426.3 mg (56%, R _f = 0.36) of the pure monoether 4 as a colorless solid. Furthermore, 82.5 mg (9%, Rf = 0.73) of the pure diether and 165.9 mg (30%, R _f = 0.15) of the educt were obtained.

Spectroscopic data for 4- (2,2,2) -ethfluoroethoxy-diamantan-9-ol: 1 H-NMR (400 MHz, CDCl ₃ ) δ: 3.79 (2H, q, J = 8.8 Hz), 2.01 -1.90 (6H , m), 1.83-

1.72 (12H, m), 1.33 (1H, OH, br s)

¹³ C-NMR (100 MHz, CDCl ₃ ) δ: 124.3 (q, J = 277.7 Hz), 73.1, 67.1, 59.3 (q, J =

35.2 Hz), 44.5, 40.3, 38.8, 38.3

¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ: -74.55 IR data (KBr): 3277.7, 2925.2, 2903.5, 2888.6, 2854.7, 1444.5, 1417.6, 1349.6,

1301 .0, 1278.4, 1 146.2, 1 103.7, 1007.8, 962.0, 836.0, 663.0 cm ^"1

Melting point: 149 ° C

HRMS: calculated for Ci ₆ H ₂ i F ₃ O ₂ : 302.1494; found: 302.1489

C, H, N: calculated for C ₁₆ H ₂ F ₃ i O ₂ (302,32): C 63.56, H 7:00; found: C 63.30, H 6.90 Embodiment 3

Preparation of 2-chloro-r / [9- (2,2,2-trifluoroethoxy) -diamantan-4-yl] -acetamicl

6.48 mmol (1.96 g) of 4- (2,2,2) -trifluoroethoxy-diamantan-9-ol 4 with a purity of> 99% were dissolved in 30 ml of glacial acetic acid and treated at room temperature with 9 ml of (0, 1 mol) of chloroacetonitrile. Thereafter, with stirring and ice bath cooling 4.5 ml of conc. Sulfuric acid added. The clear solution was then stirred for another 30 min in an ice bath and 17 h at room temperature. By adding 120 ml of dist. Water gave a colorless precipitate which was dissolved by extraction four times with 50 ml CHCl ₃ each. The combined organic phases were distilled twice with 75 ml. Washed water and dried over Na 2 SO. ₄ After filtering off the drying agent and removing the solvent, a beige, solid crude product was obtained. The crude product was separated on silica gel with CH ₂ Cl ₂ : ethyl acetate 85:15 as eluent. This gave 1.01 g (R _f = 0.57) of the pure product. After further separation of a mixed fraction on silica gel with EthenPentan 2: 1, a further 97.4 mg (R _f = 0.38) of the product were obtained. A total of 1, 1 1 g (total yield 45%) of 2-chloro-A / - [9- (2,2,2-trifluoroethoxy) diamantan-4-yl] -acetamide 5 were thus obtained. In addition, the following by-products could be isolated by various separation methods:

4-Acetoxy-9- (2,2,2-trifluoroethoxy-diamantane: 108 mg (5%) by CH ₂ Cl ₂ : ethyl acetate separation (R _f = 0.69) Bis-4,9-acetoxy-diamantane: 19 mg (1%) by the CH ₂ Cl ₂ : ethyl acetate separation

2-Chloro-Λ / - [9-acetoxy-diamantan-4-yl-1-acetamide: 237 mg (11%) by CH ₂ Cl ₂ : ethyl acetate separation (R _f = 0.41)

4- (2,2,2) -trifluoroethoxy-diamantan-9-ol: 105 mg (5%) of the starting material by the CH ₂ Cl ₂ : ethyl acetate separation (R _f = 0.26)

2-Chloro-N- [9- (2-chloro-acetylamino) diamantan-4-yl-1-acetamide: 1 16 mg (5%) by the CH ₂ Cl ₂ : ethyl acetate separation (R _f = 0.24), and further purification on silica gel with ethyl acetate as eluant (eluted with MeOH from column)

4-Acetoxy-diamantan-9-ol: 35 mg (2%) through the CH ₂ Cl ₂ : ethyl acetate separation (R _f = 0.24), and further purification on silica gel with ethyl acetate as eluant (R _f = 0.43) followed by HPLC Purification on a diol phase with f-butyl methyl ether hexane (8: 2) as a run medium

Spectroscopic data for 2-chloro-Λ / -r9- (2,2,2-trifluoroethoxy) -diamantan-4-yl1-acetamide:

¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.24 (1H, br s, NH), 3.94 (2H, s), 3.79 (2H, q, J =

8.8 Hz), 2.10-2.00 (9H, m), 1.91 (3H, br s), 1.81 -1.76 (6H, m)

¹³ C-NMR (100 MHz, CDCl ₃ ) δ: 164.9, 124.3 (q, J = 277.7 Hz), 73.0, 59.3 (q, J =

34.2 Hz), 50.8, 42.9, 40.50, 40.46, 38.3, 37.4 1 ⁹ F NMR (376 MHz, CDCl ₃ ) δ: -74.55

IR data (KBr): 3294.3, 2931.9, 2893.5, 2862.4, 1690.5, 1663.9, 1555.3, 1444.9,

141 1.3, 1353.0, 1291.8, 1 172.1, 1 109.6, 965.2, 799.3 cm ^"1

Melting point: 148 ° C

HRMS: calculated for C ₁₈ H ₂₃ CIF ₃ NO _2: 377.1369; found: 377.1346 C, H, N: calculated for Ci ₈ H ₂₃ CIF ₃ NO ₂ (377.83): C 57.22, H 6.14, N 3.71; found:

C 56.91, H 6.04, N 3.40 Spectroscopic data for 4-acetoxy-9- (2,2,2) -trifluoroethoxy-diamantane: 1 H-NMR (400 MHz, CDCl ₃ ) δ: 3.79 (2H, q, J = 8.8 Hz), 2.16-2.11 (6H , m), 2.03 (3H, br s), 1.99-1.93 (6H, m), 1.80-1.75 (6H, m)

¹³ C-NMR (100 MHz, CDCl ₃ ) δ: 170.4, 124.3 (q, J = 277.7 Hz), 78.7, 73.1, 59.3 (q, J = 34.2 Hz), 40.4, 40.3, 38.7, 38.4 1 ⁹ F NMR (376 MHz, CDCl ₃ ) δ: -74.56

IR data (KBr): 2928.7, 2887.3, 1725.2, 1468.2, 1444.6, 1369.5, 1349.9, 1294.7, 1282.0, 1237.8, 1 151.3, 1 1 15.2, 1078.5, 1017.9, 977.5, 948.3, 691.7 cm ^-1 melting point: 127 ° C HRMS: calculated for Ci ₈ H ₂₃ F ₃ O ₃ : 344.1599; found: 344.1571

C, H, N: calculated for C ₁₈ H ₂₃ F ₃ O ₃ (344.37): C 62.78, H 6.73; found: C 62.52, H 6.65

Spectroscopic data for 2-chloro-Λ / -r9-acetoxy-diamantan-4-yl1-acetamide:

¹ H-NMR (600 MHz, CDCl ₃ ) δ: 6.24 (1 H, br s, NH), 3.94 (2H, s), 2.14-2.1 1 (6H, m),

2.05-2.03 (6H, m), 2.01 (3H, br s), 1.98-1.95 (6H, m)

¹³ C-NMR (150 MHz, CDCl ₃ ) δ: 170.4, 164.9, 78.8, 50.9, 42.9, 40.64, 40.58, 38.6,

37.4, 22.7 IR data (KBr): 3412.8, 2886.1, 1723.1, 1671.4, 1524.5, 1447.8, 1354.6, 1260.7,

1232.8, 1082.7, 1027.1, 859.2, 755.3, 520.4 cm ^"1

Melting point: 195 ° C

HRMS: calculated for Ci ₈ H ₂₄ CINO ₃ : 337.1445; found: 337.1416

C, H, N: calculated for C ₁₈ H ₂₄ CINO ₃ (337.84): C 63.99, H 7.16, N 4.15; found: C 63.85, H 7.01, N 3.75

Spectroscopic data for 4-acetoxy-diamantan-9-ol:

¹ H-NMR (400 MHz, CDCl ₃ ) O: 2.16-2.1 1 (6H, m), 2.01-1.92 (9H, m), 1.76-1.72 (6H, m), 1.35 (1H, s, OH)

¹³ C-NMR (100 MHz, CDCl ₃ ) δ: 170.4, 79.0, 67.1, 44.5, 40.5, 38.7, 38.5, 22.7 IR data (KBr): 3586.9, 3443.5, 2897.7, 2884.6, 1726.4, 1447.7, 1366.6, 1346.8 , 1260.4, 1234.0, 1 122.0, 1083.1, 1027.8, 958.1 cm ^-1 melting point: 151 ° C HRMS: calculated for Ci ₆ H ₂₂ O ₃ : 262.1569; found: 262.1552

C ₁ H ₁ N: calculated for C ₁₆ H ₂₂ O ₃ (262.34): C 73.25, H 8.45; found: C 73.08, H

8:37

Embodiment 4

Preparation of 9- (2,2,2-trifluoroethoxy) diamantan-4-amine

5 6

0.48 mmol (180 mg) of 2-chloro-Λ / - [9- (2,2,2-trifluoroethoxy) -diamantan-4-yl] -acetamide 5 with a purity of> 98% were mixed with 49.5 mg (0.65 mmol) thiourea, 4 ml of ethanol and 1, 4 ml of glacial acetic acid for 16.5 hours under reflux. Thereafter, the reaction solution was distilled with 25 ml. Diluted with water and made alkaline with 4 ml of 10% NaOH. The aqueous solution was extracted three times with 20 ml of CHCl ₃ each time and the combined organic phases were washed twice with 20 ml each of dist. Washed water and dried over Na ₂ SO ₄ . Filtration of the drying agent and evaporation of the solvent gave 133.7 mg (93%) of a slightly yellowish oil which crystallized after some time.

Spectroscopic Data for 9- (2,2,2) -Thfluoroethoxy-diamantane-4-amine 6: 1 H-NMR (400 MHz, CDCl ₃ ) δ: 3.80 (2H, q, J = 8.8 Hz), 1.93 (3H, br s), 1.86 (3H, br s), 1.80-1.75 (6H, m), 1.65-1.58 (6H, m), 1.16 (2H, NH ₂ , br s) 1 ³ C-NMR (100 MHz, CDCI ₃ ) δ: 124.4 (q, J = 277.7 Hz), 73.3, 59.3 (q, J = 34.2 Hz), 45.7, 45.6, 40.6, 38.4, 38.0 ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ: -74.55

IR data (KBr): 3330.2, 2920.7, 2890.6, 1636.9, 1590.8, 1441, 6, 1288.6, 1155.9,

1 115.0, 1047.8, 101 1.7, 976.9, 668.1 cm .- ^"1 mp 1 10-1 19 ° C HRMS: Calculated for C ₆ H ₂₃ F ₃ NO: 301.1654, Found: 301.1664

Embodiment 5: Preparation of 4-amino-9-diamantanecarboxylic acid from 9- (2,2,2-trifluoroethoxy) diamantan-4-amine

6 7

2.3 mmol (700 mg) of 9- (2,2,2-trifluoroethoxy) -diamantan-4-amine 6 with a purity of> 98% were poured into an ice-cooled mixture of 40 ml of conc. Sulfuric acid and three ml of 100% formic acid. Thereafter, a further 7 ml of 100% formic acid were added dropwise within 30 min. Four hours after complete addition and stirring in an ice bath, the reaction mixture was added to 200 g of ice. This resulted in a beige, fine precipitate after 10 minutes. This was filtered off with suction through a Buchner funnel, with about 50 ml of dist. Washed water and dried over phosphorus pentoxide in a desiccator. This gave 453.2 mg of the slightly beige amino acid 7 in the form of the sulfate salt

Spectroscopic data for 4-amino-9-diamantanecarboxylic acid 7: 1 H-NMR (400 MHz, NaOD in D ₂ O) δ: 1.87-1.74 (12H, m), 1.61-1.56 (6H, m) ¹³ C-NMR (100 MHz, NaOD in D ₂ O) δ: 192.7, 49.7, 49.1, 44.6, 44.1, 42.2, 40.7 IR data (KBr): 3449.0, 2890.1, 2695.6, 2639.3, 2584.7, 2183.6, 1696.9, 1532.9, 1512.1, 1469.7, 1446.9, 1384.8, 1292.0, 1251.1, 1137.0, 1082.5, 1036.7, 620.2, 599.7, 464.6 cm ^-1 melting point :> 310 ° C HRMS: calculated for Ci ₅ H ₂ iNO ₂ : 247.1572; found: 247.1573 (as zwitterion)

Embodiment 6: Preparation of 4-trifluoroacetoxy-9- (2-chloroacetylamino) -diamantane from 2-chloro- / V- [9- (2,2,2-trifluoroethoxy) -diamantan-4-yl] -acetamide

8th

1, 06 mmol (400 mg) of 2-chloro-Λ / - [9- (2,2,2-thfluoroethoxy) diamantan-4-yl] -acetamide 5 with a purity of> 99% were dissolved in 6 ml of trifluoroacetic acid and heated at reflux for 4 h. Thereafter, the solvent was removed on a rotary evaporator to dryness. The colorless, solid crude product was separated on silica gel with diethyl ether as the eluent. This gave 402 mg (97%, R _f = 0.45) of the pure product as a colorless solid.

Spectroscopic data for 4-trifluoroacetoxy-9- (2-chloroacetylamino) -diamantane 8: ¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.27 (1H, s, NH), 3.96 (2H, s), 2.25- 2.20 (6H, m), 2.17-2.06 (9H, m), 2.02 (3H, br s) ¹³ C-NMR (100 MHz, CDCl ₃ ) δ: 165.0, 156.0 (q, J = 41.3 Hz), 1 14.3 (q, J = 287.8 Hz), 85.4, 50.6, 42.9, 40.3, 40.2, 38.7, 37.1 1 ⁹ F-NMR (376 MHz, CDCl ₃ ) δ: -75.75

IR data (KBr): 3415, 2941, 2903, 1767, 1674, 1530, 1213, 1 164, 1077, 853, 775 cm ^-1

Melting point: 172 ° C

HRMS: calculated for C ₁₈ H _2I CIF ₃ NO ₃ : 391.1 162; found: 391.1 163 C ₁ H ₁ N: calculated for Ci ₈ H ₂₁ CIF ₃ NO ₃ (391.81): C 55.18, H 5.40, N 3.57; found: C 55.21, H 5.27, N 3.48

Embodiment 7: Preparation of 4-aminodiamantan-9-ol from 4-trifluoroacetoxy-9- (2-chloroacetylamino) diamantane

8th

1, 62 g (4.12 mmol) of 4-trifluoroacetoxy-9- (2-chloroacetylamino) diamantane 8 were mixed with 474 mg (6.23 mmol) of thiourea and dissolved in a mixture of 20 ml of ethanol and 15 ml of acetic acid. The solution was refluxed for 4 hours and, after cooling to room temperature, diluted with 60 ml of a 20% aqueous NaOH solution. After four extractions with 80 ml_ CHCI ₃ , washed twice with 80 ml_ distilled water and Drying over anhydrous Na ₂ SO _{4 gave} 781 mg (86%) of the aminoalcohol 9 as a colorless solid.

Spectroscopic data for 4-amino-diamantan-9-ol: 1 H NMR (400 MHz, CDCl ₃ ) δ: 1.89-1.79 (6H, m), 1.74-1.68 (6H, m), 1.61-1.56 (6H, m ), 1.49-1.24 (3H, m, OH + NH ₂ )

¹³ C-NMR (100 MHz, CDCl ₃ ) δ: 67.2, 45.8, 45.7, 44.8, 38.8, 37.9 IR data (KBr): 3241, 2920, 2887, 2849, 1584, 1470, 1439, 1352, 1254, 1 122, 1082, 1045, 1032, 970, 919 cm ^-1 melting point: 240-244 ° C

HRMS: calculated for Ci ₄ H ₂₁ NO: 219.1623; found: 219.1628

C, H, N: calculated for C ₁₄ H ₂₁ NO (219.32): C 76.67, H 9.65, N 6.39; found: C

76.57, H 9.65, N 6.33

Embodiment 8:

Preparation of 4-nitrodiamantan-9-ol

4-Aminodiamantan-9-ol

9 10

1.74 mmol (300 mg) of mete-chloroperbenzoic acid (m-CPBA) were dissolved in 20 ml of 1,2-dichloroethane and heated under reflux. A solution of 0.46 mmol (100 mg) of 4-amino-diamantan-9-ol 9 in 10 mL of 1, 2-dichloroethane was added dropwise and rinsed with 5 mL of 1, 2-dichloroethane. The clear solution was refluxed for 3 h. It was then cooled to room temperature and the organi- see phase washed three times with 60 ml_ of a 10% aqueous NaOH solution and dried over Na ₂ SO ₄ . After filtering off the drying agent and removing the solvent, a colorless, solid crude product was obtained. This was purified on silica gel with ether as eluent. This gave 101.3 mg (89%, R _f = 0.19) of the pure nitroalcohol 10 as a colorless solid.

Spectroscopic data for 4-nitrodiamantan-9-ol:

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 2.22-2.17 (6H, m), 2.03-1.92 (6H, m), 1.74-1.68 (6

H, m), 1.33 (1 H, br s, OH) 1 ³ C-NMR (100 MHz, CDCl ₃ ) δ: 83.4, 66.7, 44.3, 40.3, 38.2, 37.5

IR data (KBr): 3311.8, 2921.5, 2885.4, 1529.5, 1474.8, 1445.6, 1364.4, 1251.6,

1 107.3, 1082.1, 1050.5, 868.8, 802.9 cm ^"1

Melting point: 172 ° C

C ₁ H ₁ N: calculated for C ₁₄ H ₁₉ NO ₃ (249.31): C 67.45, H 7.68, N 5.62; found: C 67.42, H 7.69, N 5.52

Exemplary embodiment 9: Preparation of 4-amino-9-diamantanecarboxylic acid from 4-aminodiamantan-9-ol

Oleum, HCOOH

9 7

20 mL oleum was added under cooling in an ice-salt bath with 1 mL 100%

Formic acid added. With stirring, 200 mg (0.91 mmol) of 4-amino-9-diamantanol 9 and subsequently 1 mL of formic acid were added. After 15 min, a clear solution was formed and in the course of 1 h, a further 3 mL HCOOH added dropwise. After another hour of stirring at RT, the solution was added to 150 g of ice and carefully mixed with 60 ml_ of a 30% NaOH solution. This resulted in a colorless precipitate, which was sucked off over a Buchner funnel, with 30 ml dest. Washed water, and over P ₂ O _{5 was} dried. In this case 190 mg of the amino acid 7 were obtained as sulfate salt.

Spectroscopic data for 4-amino-9-diamantane carboxylic acid are shown in Example 5.

Embodiment 10:

Preparation of 4-amino-9-diamantancarbonsäuremethylester from

4-Aminodiamantan-9-ol

e

9 11

250 mg (1.14 mmol) of 4-amino-9-diamantanol 9 were dissolved in 20 ml of oleum and cooled in an ice-salt bath at about 0 ° C. 7 mL of 100% formic acid were added dropwise to this solution within 1 h. The mixture was then stirred for 1 h at RT and then added to 100 g of ice. To the clear solution was added 40 mL of a 30% NaOH solution to give a colorless precipitate. The precipitate was filtered off through a Buchner funnel, with 30 mL dist. Washed water and dried over P ₂ O ₅ . The resulting 242 mg of the crude product were then heated under reflux with 3 ml of thionyl chloride and 15 drops of pyridine as catalyst for 30 min. Thereafter, the excess SOCl ₂ was distilled off in vacuo and 3 ml of absolute methanol were added to the crude product (strong gas evolution). After stirring for 20 minutes, the solvent was stripped off and the oily crude product with 15 ml of saturated NaHCO ₃ Solution and 50 ml dist. Water is added. The aqueous phase was extracted three times with 60 ml CHCI ₃ each time and the combined organic phases with 60 ml dest. Washed water, and dried over Na ₂ SO ₄ . After filtering off the drying agent and removing the solvent, 175 mg of a brown solid were obtained. This was sublimed for purification in a high vacuum to give 12 mg (0.43 mmol, 38%) of the pure product.

Spectroscopic data for methyl 4-amino-9-diamantanecarboxylate 11: ¹ H-NMR (600 MHz, CDCl ₃ ) δ: 3.68 (3H, s), 1.94-1.89 (6H, m), 1.87 (3H, br s), 1.81 (3H, br s), 1.63-1.58 (6H, m), 1.24 (2H, NH ₂ , br s)

¹³ C-NMR (150 MHz, CDCl ₃ ) δ: 178.2, 51.6, 46.1, 45.8, 38.86, 38.84, 38.1, 36.1 IR data (KBr): 3344.3, 3280.7, 2956.4, 2915.9, 2879.8, 2864.0, 1730.0, 1596.5 , 1461.5, 1442.2, 1353.7, 1280.3, 1228.5, 1095.3, 1043.7, 867.1 cm ^"1 melting point: 1 17 ⁰ C HRMS: calculated for C ₆ H ₂₃ NO _2: 261.1729, found: 261.1731

C ₁ H ₁ N: calculated for C ₁₆ H ₂₃ NO ₂ (261.36): C 73.53, H 8.87, N 5.36; found: C 73.41, H 8.94, N 5.03

Embodiment 11:

Preparation of 4-amino-9-diamantanecarboxylic acid hydrochloricl

4-amino-9-diamantancarbonsäuremethylester

11 ₁₂ 0.23 mmol (60 mg) of methyl 4-amino-9-diamantanecarboxylate 11 were dissolved in 3 ml of conc. Dissolved hydrochloric acid and heated for 3 h at reflux. It was then cooled to RT, whereupon colorless crystals precipitated. These were filtered off with suction and dried on a rotary evaporator. There were obtained 34.2 mg of the colorless product. Concentration of the filtrate to dryness gave an additional 25.2 mg of the product. In total, 59.4 mg (91%) of 4-amino-9-diamantanecarboxylic acid hydrochloride 12 were obtained.

Spectroscopic data for 4-amino-9-diamantanecarboxylic acid hydrochloride:

¹ H NMR (400 MHz, DMSOD ₆ ) δ: 12.09 (1 H, s, COOH), 8.06 (3 H, s, NH ₃ ), 1.86 (3 H, br s), 1.81-1.71 (15 H, m)

¹³ C-NMR (100 MHz, CDCl ₃ ) δ: 178.5, 49.9, 40.1 (from DEPT135), 38.4, 37.6, 36.6,

35.3

IR data (KBr): 341 1.8, 3147.4, 2925.5, 2890.3, 2860.8, 2612.7, 2552.1, 2459.2,

1978.6, 1715.6, 1699.1, 1614.5, 1598.4, 1517.5, 1352.7, 1288.1, 1236.3, 1200.7, 1096.2 cm ^-1

Melting point:> 350 ° C

C ₁ H ₁ N: calculated for Ci ₅ H ₂₂ CINO ₂ (283.79): C 63.48, H 7.81, N 4.94; found:

C 63.30, H 8.02, N 4.75 Embodiment 12:

Preparation of 4- (2,2,2-trifluoro-1-trifluoromethyl-ethoxy) -diamantan-9-ol

1,1,1,3,3,3-hexafluoro-propan-2-ol, CF ₃ SO ₃ H

2. triethylamine

13.1, 13 mmol (250 mg) 4,9-Diamantandiol 3 with a purity of> 99% were in 8 ml_ 1, 1, 1, 3,3,3-hexafluoro-propan-2-ol given. To this was added 3 μl of trifluoromethanesulfonic acid. The colorless suspension was stirred for 45 min at room temperature and then admixed with 50 μl of triethylamine. After removal of the solvent, the solid, colorless crude product was separated on silica gel with ethyl acetate: hexane (8: 2) as eluent. This gave 134 mg (32%, R _f = 0.38) of the pure monoether 13 as a colorless solid. Furthermore, 101.7 mg (17%, R _f = 0.77) of the pure diether and 107.9 mg (43%, R _f = 0.18) of the educt were obtained.

Spectroscopic data for 4- (2,2,2-thifluoro-1-trifluoromethylethoxy) diamantan-9-ol 13:

¹ H-NMR (600 MHz, CDCl ₃ ) δ: 4.34 (1 H, septet, J = 6.0 Hz), 1.97 (3H, br s), 1.92 (3H, br s), 1.82-1.78 (6H, m) , 1.75-1.71 (6H, m), 1.33 (1H, s, OH) 1 ³ C-NMR (150 MHz, CDCl ₃ ) δ: 121.6 (q, J = 283.7 Hz), 77.5, 68.2 (Septet, J = 32.2 Hz), 66.9, 44.3, 40.9, 38.54, 38.52 1 ⁹ F NMR (376 MHz, CDCl ₃ ) δ: -73.34

IR data (KBr): 3278.9, 2924.5, 2880.6, 2862.2, 1445.6, 1359.6, 1282.3, 1251 .3, 1 194.9, 1 1, 13.9, 1096.4, 1048.4, 1005.2, 957.7, 890.1, 685.3 cnϊ -1 melting point: 163 ° C HRMS: calculated for Ci ₇ H ₂₀ F ₆ O ₂ : 370.1368; found: 370.1343

C, H, N: calculated for C ₁₇ H ₂₀ F ₆ O ₂ (370.33): C 55.14, H 5:44; found: C 55.12,

H 5.31

Embodiment 13:

Preparation of 1- (2,2,2-trifluoroethoxy) diamantan-6-ol

1 . 2,2,2-trifluoroethanol, CF ₃ SO ₃ H, Δ

2. triethylamine

14 15

1, 13 mmol (250 mg) of 1, 6-Diamantandiol 14 with a purity of> 99% were dissolved in 40 ml of 2,2,2-trifluoroethanol and treated at 40 ° C in a water bath with 25 ul_ CF ₃ SO ₃ H. After stirring for 20 minutes at the same temperature, the acid was neutralized with 100 μl of triethylamine and the solvent was stripped to dryness. The colorless, solid crude product was separated on silica gel with ethyl acetate: hexane 8: 2 as eluent. This gave 220 mg (64%, R _f = 0.54) of the pure monoether 15 as a colorless solid. Furthermore, 64 mg (15%, R _f = 0.72) of the pure diether were obtained.

Spectroscopic Data for 1 - (2,2,2) -Thfluoroethoxy-diamantan-6-ol 15:

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 3.65 (2H, q, J = 8.4 Hz), 2.14-1.97 (6H, m), 1.89 (2H, s), 1.75 (2H, s), 1.63- 1.57 (4H, m), 1.36-1.27 (4H, m), 1.21 (1H, OH, br s) ¹³ C-NMR (100 MHz, CDCl ₃ ) δ: 124.5 (q, J = 277.7 Hz), 75.6 , 70.3, 58.8 (q, J = 34.2 Hz), 46.1, 44.8, 41.8, 39.6, 31.5, 31.4, 29.4, 29.1 1 ⁹ F NMR (376 MHz, CDCl ₃ ) δ: -74.14

IR data (KBr): 3264.2, 2913.9, 2903.9, 1463.6, 1346.3, 1290.8, 1271.8, 1 157.3, 1105.5, 1007.6, 966.7, 895.3, 679.2 cm ^-1 melting point: 124 ° C HRMS: calculated for Ci ₆ H _2I F ₃ O ₂ : 302.1494; found 302.1475

C ₁ H ₁ N: calculated for C ₁₆ H ₂₁ F ₃ O ₂ (302.32): C 63.56, H 7.00; found: C 63.64, H

7:00

Embodiment 14:

Preparation of 9- (2,2,2-trifluoroethoxy) -triamantan-15-ol

1. 2,2,2-trifluoroethanol, CF ₃ SO ₃ H

2. triethylamine

16 17

0.15 mmol (40.8 mg) of 9,15-triamantanediol 16 with a purity of> 99% were dissolved in 20 ml of 2,2,2-trifluoroethanol and 5 μl CF ₃ SO ₃ H were added at room temperature. After stirring at the same temperature for 14 h, the acid was neutralized with 10 μl of triethylamine and the solvent was stripped to dryness. The slightly oily crude product was separated on silica gel with ethyl acetate: hexane 8: 2 as eluent. This gave 28.0 mg (53%, R _f = 0.49) of the pure monoether 17 as a colorless solid. Furthermore, 17.5 mg (27%, R _f = 0.72) of the pure diether and 5.1 mg (13%, R _f = 0.15) of the educt were obtained.

Spectroscopic Data for 9- (2,2,2) -Thfluoroethoxy-diamantan-15-ol 17:

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 3.79 (2H, q, J = 8.8 Hz), 2.05-1.92 (4H, m), 1.81 -

1.60 (12H, m), 1.44-1.31 (7H, m)

¹³ C-NMR (100 MHz, CDCl ₃ ) δ: 124.4 (q, J = 277.7 Hz), 73.9, 67.9, 59.3 (q, J =

34.2 Hz), 52.0, 47.7, 45.2, 44.5, 41.1, 39.5, 39.2, 38.5, 36.3, 33.8, 33.5

¹⁹ F NMR (376 MHz, CDCl ₃ ) δ: -74.54

IR data (KBr): 3304.4, 2917.7, 2900.3, 2874.7, 2850.7, 1443.9, 1339.3, 1281.4,

1 156.7, 1 146.1, 1 122.1, 1 1 12.0 cm -1 Melting point: 153 ° C

HRMS: calculated for C ₂₀ H ₂₅ F ₃ O ₂ : 354.1807; found: 354.1773

C ₁ H ₁ N: calculated for C ₂₀ H ₂₅ F ₃ O ₂ (354.41): C 67.78, H 7.1 1; found: C 67.69, H

7.16

Embodiment 15:

Preparation of 6- (2,2,2-trifluoroethoxy) -anti-tetramantan-13-ol

1 . 2,2,2-trifluoroethanol, CF ₃ SO ₃ H

2. triethylamine

18 19

0.3 mmol (97.3 mg) of 6,13-antf-tetramantanediol 18 with a purity of> 99% were dissolved in 36 ml of 2,2,2-trifluoroethanol and treated at room temperature with 9 μl CF ₃ SO ₃ H. After stirring for 2 h at the same temperature, the acid was neutralized with 20 .mu.l of triethylamine and the solvent was evaporated to dryness. The colorless, solid crude product was separated on silica gel with ethyl acetate: hexane 8: 2 as eluent. This gave 75.7 mg (62%, R _f = 0.48) of the pure monoether 19 as a colorless solid. Furthermore, 34.2 mg (23%, Rf = 0.77) of the pure diether and 12.2 mg (13%, R _f = 0.32) of the educt were obtained.

Spectroscopic data for 6- (2,2,2) trifluoroethoxy-anf / tetramantan-13-ol 19: ¹ H-NMR (400 MHz, CDCl ₃ ) δ: 3.79 (2H, q, J = 8.8 Hz), 1.97-1.87 (4H, m), 1.80-1.63 (1 OH, m), 1.45-1.27 (13H, m) ¹³ C-NMR (150 MHz, CDCl ₃ ) δ: 124.4 (q, J = 277.7 Hz), 74.3, 68.3, 59.2 (q, J = 34.7 Hz), 51.3, 47.1, 45.4, 45.2, 45.1, 44.3, 44.1 , 40.9, 40.3, 39.9, 35.2, 35.0, 33.6, 33.5

¹⁹ F-NMR (376 MHz, CDCl ₃ ) δ: -74.54 IR data (KBr): 3268.0, 2901.5, 2879.5, 1465.4, 1446.5, 1418.8, 1338.8, 1282.6, 1 159.0, 1 147.9, 1 122.7, 1 1 12.6 , 1071.1, 1029.0, 1004.3, 991.7, 969.2, 866.3, 763.7 cm ^"1

Melting point: 169 ° C HRMS: Calculated for C ₂₄ H ₂₉ F ₃ O _2: 406.2120; found: 406.2106

Claims

claims

1. Functionalized diols of the diamondoids according to formula (I), in which one of the two hydroxyl groups is masked by a protective group,

wherein

- D stands for a diamondoid,

R ^{1 is} a linear or branched alkyl group -C _π H _p X _q ,

^■ where n is a natural number from 1 to 25, ■ p is an integer between 0 and 50, and q is a natural number between 1 and 51,

^■ and the sum of q and p (2n + 1),

R ^{2 is} hydrogen or a linear or branched alkyl group -C _m H _r X _s , where m is a natural number from 1 to 25,

^■ r and s are integers between 0 and 51,

^■ and the sum of r and s (2m + 1),

X is a halogen selected from fluorine, chlorine or bromine,

R ³ , R ⁴ , R ⁵ and R ⁶ independently represent hydrogen, a linear or branched alkyl group of 1 to 20 carbon atoms, a cyclic alkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 18 carbon atoms, a heteroaryl group of 5 up to 18 ring atoms, of which 1 or 2

Atoms are heteroatoms selected from nitrogen, oxygen, sulfur, and the remaining ring atoms are carbon atoms.

2. Functionalized diols of diamondoids according to claim 1, characterized qe- indicates that the halogen X in R ¹ and R ^{2 is} fluorine.

3. Functionalized diols of diamondoids according to any one of claims 1 and 2, characterized in that R ³ and R ^{4 are} hydrogen and R ⁵ and R ^{6 is} a linear or branched alkyl group having 1 to 20 carbon atoms.

4. Functionalized diols of the diamondoids according to one of claims 1 to 3, characterized in that R ³ and R ^{4 are} hydrogen and R ⁵ and R ^{6 are} identical.

5. Functionalized diols of the diamondoids according to one of claims 1 to 4, characterized in that R ³ and R ^{4 are} hydrogen, R ⁵ and R ^{6 are} identical and R ⁵ and R ^{6 is} a linear or branched alkyl group having 1 to 20 Carbon atoms.

6. Functionalized diols of the diamondoids according to one of claims 1 to 5, characterized in that the protective group of the formula (II)

/ CH ("I)

R ^{2 contains} a total of 2 to 12 carbon atoms.

7. Functionalized diols of the diamondoids according to one of claims 1 to 6, characterized in that the protective group -CHR ¹ R ^{2 is} selected from -O-CH ₂ -CF ₃ , -O-CH ₂ -CF ₂ H, -O- CH ₂ -CF ₂ -CF ₃ , -O-CH ₂ -CF ₂ -CF ₂ H, -O-CH- (CF ₃ ) ₂ , -O-CH ₂ - (CF ₂ ) ₂ -CF ₃ , -O -CH ₂ - (CF ₂ ) ₂ -CF ₂ H, -O-CH ₂ - (CF ₂ ) S-CF ₃ , -O-CH ₂ - (CF ₂ ) S-CF ₂ H.

8. Functionalized diols of diamondoids according to one of claims 1 to 7, characterized in that D is a lower diamondoid selected from adamantane, diamantane and triamantane.

9. A process for the preparation of functionalized diols of the diamondoids comprising the following steps: a) mixing a diamondoid diol DR ³ R ⁴ R ⁵ R ⁶ (OH) 2 with a halogenated alcohol CHOHR ¹ R ² , where D, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ b) adding a catalyst acid, c) stirring at -20 ° C to 100 ° C, d) terminating the reaction by adding an amine or water, e) isolating the crude end product, f) purifying the final product.

A process for the preparation of functionalized diols of the diamondoids according to claim 9, characterized in that the alcohol CHOHR ¹ R ^{2 is} selected from -O-CH ₂ -CF ₃ , -O-CH ₂ -CF ₂ H, -O-CH ₂ -CF ₂ -CF ₃ , -O-CH ₂ -CF ₂ -CF ₂ H, -O-CH- (CF ₃ ) ₂ , -O-CH ₂ - (CF ₂ ) ₂ -CF ₃ , -O- CH ₂ - (CF ₂ ) ₂ -CF ₂ H.

11. A process for the preparation of functionalized diols of the diamondoids according to any one of claims 9 and 10, characterized in that the catalyst acid in step c) is selected from CF ₃ SO ₃ H and p-toluenesulfonic acid.

12. A process for the preparation of functionalized diols of the diamondoids according to any one of claims 9 to 1 1, characterized in that the termination of the reaction according to step d) is carried out by adding an amine.

13. A process for the preparation of functionalized diols of the diamondoids according to one of claims 9 to 1 1, characterized in that the

Ending the reaction according to step d) is carried out by adding water.

14. Use of functionalized diols of the diamondoids according to any one of claims 1 to 8 for the preparation of monoether amides according to formula (V)

wherein R ^{7 is} a linear, branched or cyclic alkylene group -C ₁ H ₂ T, t is a natural number of 1 to 1 1, Y is a halogen atom selected from fluorine, chlorine, bromine, iodine and R ¹ to R ^{6 are} as defined above, wherein a functionalized diol of a diamondoid is reacted with a nitrile YR ⁷ -CN in a Ritter reaction in the presence of concentrated sulfuric acid to the monoether amide.

15. Use of monoether amides according to claim 14, wherein R ^{2 is} a hydrogen atom, in a process for the preparation of amino alcohols of the diamondoids, comprising the steps: a) reaction of the monoether amide with trifluoroacetic acid, b) heating with thiourea , Ethanol and glacial acetic acid, c) Alkaline the reaction solution with an aqueous liquor, d) isolating and purifying the amino alcohol thus obtained.

16. Use of amino alcohols according to claim 15 in a process for the preparation of aminocarboxylic acids of the diamondoids, comprising the steps: a) reaction of the aminoalcohol with oleum and concentrated formic acid at -20 ° C and 0 ° C, b) precipitating the crude aminocarboxylic acid salt with a L) c) isolation, purification and drying of the aminocarboxylic acid salt, d) reaction with thionyl chloride and methanol to give the methyl aminocarboxylate, e) cleavage of the ester by heating with a strong mineral acid, f) separation, purification and drying of the aminocarboxylic acid.

17. Use of monoether amides according to claim 14 in a process for the preparation of aminocarboxylic acids of the diamondoids, comprising the steps: a) heating the monoether amide with thiourea, ethanol and glacial acetic acid, b) diluting the reaction solution with water, c) Alkaline d) isolating and purifying the monoether-amine thus obtained, e) reacting the monoether with concentrated sulfuric acid and 100% formic acid at temperatures between -20 ° C. and 0 ° C., f) reaction mixture from step e) put on ice, isolate and purify the aminocarboxylic acid obtained.