DE2331817A1 - Bis-aminoethyl-adamantane-diamides - as surfactants and antivirals from bis-aminoethyl-adamantane and acid derivs - Google Patents

Abstract

Cpds. of formula (I) where R=H, a monovalent 1-21C aliphatic hydrocarbon, a mo novalent alicyclic 3-10C hydrocarbon or a monovalent aromatic 6-19C hydrocarbon; pref. R = 1-18C alkyl, 10-18C alkenyl, 3-8C cycloalkyl, 4-10 bicycloalkyl, Ph (opt. substd. by 1-4C alkylene) Ph-C1-6 alkyl or naphthyl, R1, R2 (opt. identical) H or 1-4C are surface active agents, additives for lubricating oils and antivirals. Prepd. from bisaminoethyl-adamantanes and excess RCOX (X = OH, lower alkoxy, Cl or Br).

Description

1,3-bis (aminoethyl) adamantane diamides and process for their preparation Diamides of 1, 3-bis-Äminoäthylderivaten of adamantane and alkyladamantane of general formula Ad (CE2CH2NHCOR) 2 in the Ad adamantane or an alkyladamantane radical and R is hydrogen or a monovalent aliphatic, alicyclic or aromatic Hydrocarbon radicals are obtained by reacting 1,3-bis-aminoethyladamantane compounds the general formula Ad (CH2CE2NH2) 2 in the Ad has the same meaning as above owns, with a Carboxylic acid or a functional derivative the same of the general formula SCOX, in which R has the same meaning as above and X has a hydroxyl, a lower alkoxy group or a halogen represents. The diamides are used as surface-active agents, for melting textiles, useful as additives to lubricating oils and as antiviral agents.

The invention relates to new compounds of the formula in which R is a hydrogen atom, a monovalent aliphatic hydrocarbon radical having 1 to 21 carbon atoms, a monovalent alicyclic hydrocarbon radical having 3 to 10 carbon atoms or a monovalent aromatic hydrocarbon radical having 6 to 18 carbon atoms and R1 and R2, which can be the same or different, hydrogen or denote an alkyl radical having 1 to 4 carbon atoms.

As far as the applicant was able to determine, they contain adamantane rings Diamides of the formula given above are new compounds, the neither are described in a patent or in scientific literature so far.

The new compounds are valuable for several purposes, in particular as surface-active agents, as flux agents for textiles, as additives for lubricating oils and the like and as antiviral pharmaceuticals.

The new compounds of the formula I can be prepared by reacting 1 bis-aminoethyl-adamantane compounds of the following formula in which R1 and R2 have the same meaning as in formula I are prepared with a carboxylic acid or a functional derivative thereof of the formula RCOX III, in which R has the same meaning as in formula I and X is a hydroxyl or lower alkoxy group or a halogen like chlorine or bromine means.

The carboxylic acid used in the present invention and its functional derivatives of Formula III include formic acid, all straight chain and branched chain aliphatic carboxylic acids having 1 to 21 carbon atoms in the R group, alicyclic carboxylic acids with 3 to 10 carbon atoms in the R group and aromatic carboxylic acids with 6 to 18 carbon atoms in the R group as well as acid halides and lower alkyl esters of these acids, in which the lower Alkyl group has 1 to 4 carbon atoms.

The preferred aliphatic carboxylic acids are alkyl or alkenyl carboxylic acids with 1 to 18 carbon atoms in the alkyl or alkenyl group are used, in particular Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Isobutyric acid and isovaleric acid. As the aliphatic carboxylic acid are preferred 2cloalkanecarboxylic acids with 3 to 8 carbon atoms in the R group and bicycloalkanecarboxylic acids with 4 to 10 carbon atoms in the R group used, in particular cyclopentanecarboxylic acid, Cyclohexanecarboxylic acid, cyclohexyl acetic acid and 1- or 2-carboxydecaline. As aromatic Carboxylic acids are preferably honocarboxylic acids of the benzene series and the naphthalene series used, in which R is a phenyl group, one with up to 3 alkyl radicals from 1 to 4 carbon atoms substituted phenyl group, also # vU-Phenylalkylcarbonsäureq in which the alkyl group has 1 to 6 carbon atoms, or a ì4aphthyl group and in particular benzoic acid, phenylacetic acid and α- or / 2-naphthoic acid.

The adamantane-containing diamines used in the present invention of formula II include, for example, 1,3-bis-aminoethyladamantane and its derivatives, in those in the 5- or 7-position of the adamantane ring substituents from lower Alk; groups with 1 to 4 carbon atoms are present. Examples of with lower Alkylene substituted adamantane groups are: 5-methyladamantane-1,3-, 5-ethyladamantane-1,3-, 5,7-dimethyladamantane-1,3- and 5-methyl-7-ethyladamantane-1,3-.

The compounds of formula I, i.e. the end products of the present Invention are easily made by reacting 1,3-bis-aminoethyladamantane of the formula II with carboxylic acids or their functional derivatives of the formula III in known Way, as described in more detail below.

The end products of formula I can by dehydration between a carboxylic acid of the formula RCOOH and 1,3-bis-Aminoäthyladamantan at increased Temperatures with or without the use of a catalyst or by aminolysis of a Esters are obtained with these diamines, preferably at low temperatures, to allow the diamide formed to crystallize out.

If an acid halide is used as the compound of the formula III, the desired diamides of the formula I can be obtained by reacting the acid halides with 1,3-bis-aminoethyladamantanes in a suitable inert solvent in the presence a tertiary amine or with the help of the Schotten-Baumann reaction of the two reactants in the presence of an aqueous caustic alkali solution in the heterogeneous Sgstem received.

In both processes it is generally advantageous to use an excess to use of carboxylic acid or its functional derivative to reduce the reaction time to shorten, although the object of the invention can be achieved by considering the reactants used in essentially equivalent amounts.

The method of the present invention is intended to be based on the following Examples are described in more detail.

The melting points given in the examples are not corrected.

Example 1 To a mixture of 6.6 g (0.03 Hol) of 1,3-bis-aminoethyladamantane and 30 g (0.38 pool) of pyridine, which is kept at a temperature below 1000, a mixture of 14.2 g (0.09 Hol) of caprylic acid chloride is added dropwise with stirring and 10 g of benzene added. The reaction mixture is at the specified temperature stirred for an hour, then another hour at room temperature and finally on the reflux condenser for five hours to complete the reaction heated.

300 cc of benzene are added to this reaction product and then washed one the mixture successively with water, dilute hydrochloric acid and show sodium bicarbonate solution and finally again with water. The benzene solution becomes anhydrous after drying over Concentrated sodium sulfate to make them crystallize. The crystals are purified by recrystallization from a benzene-ethano mixture. han receives 12.0 g (Yield 84.4%) of the pure amide.

Properties of the amide: Melting point: 104.5 to 105 ° C Elemental analysis: G (%) H (0%) N (%) found: 75.7 11.1 5.4 calculated: 75.89 11.47 5.90 IR spectrum (cm 1) 3280,3100: # NH 1640: s C - O (amide I absorption) 1565: # N-H (amide II absorption) Example 2 A mixture of 6.66 g (0.03 mol) of 1,3-bis-aminoethyladamantane and 14.45 g (0.06 mol) of methyl myristate are heated to a temperature of 230 to 260 ° C brought. In doing so, nitrogen is introduced into the liquid mixture. To this The ethanol formed is distilled off. After three hours the temperature will heated to 300 ° C. Heating is used for 30 minutes to complete the reaction continued, the methanol formed being distilled off.

The reaction product is obtained by recrystallization from a mixture purified from ethanol and tetrahydrofuran. flan receives 15.94 g (a yield of 83.2%) of the pure amide.

Properties of the amide: Melting point: 100 to 100.5 ° C Elemental analysis: C (%) H (%) N (%) found: 78.3 11.6 4.8 calculated: 78.44 12.2 4.36 IR spectrum: (cm 1) 3370,3340: # NH 1640: # C C = o (amide I absorption) 1535: # N-H (amide II absorption) Examples 3 to 5 A mixture of 0.06 ol of the carboxylic acid given in Table 1 and 6.66 g (0.03 mol) of 1,3-bis-Aminoäthyladamantan with 40 ccm of xylene was under Heated to reflux for eight hours, the water continuously from the azeotropic The water-xylene mixture was removed. The xylene was distilled off under reduced pressure and the residue is purified by recrystallization from a benzene-ethanol mixture.

In this process, the amides of butyric acid, stearic acid and oleic acid compounds obtained from 1,3-bis-aminoethyladamantane. The yield in all cases was over 85 C / o. Elementary Found table (%) Example carboxylic acid melting point analysis (Calculated (%)) RCOOH (° C) C H N 72.9 10.4 7.6 3 n -C3H7COOH 141-142 (72.88) (10.57) (7.73) 78.8 12.2 3.7 4 n -C17H35COOH 107.5-108 (79.51) (12.55) (3.71) 5 Oleic Acid * 45-48 ** - - - * The purity of the used Oleic acid was about 90%.

** The reaction product was not purified.

IR spectrum (cm-1) 3200, 3100: # NH 3010 (shoulder): # CH (= CH-) 1620: # C C = O (amide I absorption) 1560: # N-H (amide II absorption)

Claims (2)

Claims Compounds of the formula in which R is hydrogen, a monovalent aliphatic hydrocarbon radical with 1 to 21 carbon atoms, a monovalent alicyclic hydrocarbon radical with 3 to 10 carbon atoms or a monovalent aromatic hydrocarbon radical with 6 to 18 carbon atoms and R1 and R2, which can be the same or different, hydrogen or an alkyl radical represent with 1 to 4 carbon atoms. 2. A compound according to claim 1, characterized in that R is a An alkyl group with 1 to 18 carbon atoms, an alkenyl group with 10 to 18 carbon atoms, a cycloalkyl group with 3 to 8 carbon atoms, a bicycloalkyl group with 4 to 10 carbon atoms, a phenyl group, one with alkylene phenyl group substituted from 1 to 4 carbon atoms, a phenylalkyl group, in.der the alkyl has 1 to 6 carbon atoms, or represents a liaphthyl group.