SU606853A1 - Method of preparing 1-(adamantyl-1)-propanol-1 - Google Patents

Description

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The invention relates to the field of producing an adamantane derivative, which can be used in the synthesis of physiologically active substances, polymeric materials and in fine organic synthesis.

A known method for producing isomeric 2- (adamantyl-1) - and 1- (adamantyl-1) -propanol-2.

So, 2- (adamantyl-1) -nanol-2 is obtained by Grignard reaction from methyl- (adamantyl-1) -ketone or from (adamantyl-1) carboxylic acid ester 1.

1- (Adamantyl-1) -propanol-2 is obtained by reducing (adamantyl -) - acetone with lithium aluminum hydride 2.

However, these methods are multistage due to the preparation of the corresponding carbonyl compounds, for example (adamantyl-1) acetone, starting from adamantanol-1, are prepared in five stages.

In addition, the process of obtaining isomeric (adamantyl-1) -propanol-2 in large quantities is complicated by the fact that the reactions are carried out in a highly flammable diethyl ether medium and include the preliminary preparation of organomagnesium compounds.

The closest to the invention to the technical essence is the method of obtaining

1 - (ada.mantil-1) -propanol-1 from. Chlorohydrochloride (adamantyl-1) -carboxylic acid and dipethylcadmi. The obtained ethyl- (adamantyl-1) -ketone is reduced by lithium aluminum hydride to 1- (adamantyl-1) -propanol-1. But in this process, obtaining the target product is complicated by the fact that diethylcadmium must be preliminarily synthesized from ethyl bromide; n cadmium chloride 3.

In addition, 1- (adamantyl-1) -iropacol-1 by this method does not provide a high yield (50%) and, when carried out in sufficiently large quantities, is based on the use of highly volatile and flammable ueutecTB such as ethyl bromide and diethyl ether , and the use of unstable, easily oxidizing in air (sometimes with self-ignition) diethylcadm, alumohydride lithium.

The aim of the invention is to develop a simple and convenient method for the preparation of 1- (adamantyl-1) -propanol-1 with a better yield.

Claims (3)

The goal is achieved in that adamantonol-1 is reacted with propylene in the presence of trifluoroacetic acid, preferably at 20-70 ° C, without solvent or in an inert solvent, followed by isolation of the target product using conventional methods. This method involves the use of industrial propylene, and also provides an output of up to 70 ° / o. Example 1. In a three-necked flask equipped with a reflux condenser and a gas supplying tube, add 1.2 g (0; 0079 mol) of adamantanol — 1.5 ml (0.064 mol) of trifluoroacetic acid, 15 ml of methylene chloride and at room temperature for 7 h miss 0.5 liter (0.022 mol) of dry propylene. Upon completion of the reaction, the mixture is decomposed with a dilute soda solution and extracted with ether. The ether was distilled off, 15 ml of a 20% potassium hydroxide solution was added to the residue and boiled for 4 hours, then extracted with ether. The ether extracts are washed with water until neutral, dried over magnesium sulphate and the ether is distilled off. The residue (1.24 g) according to GLC data contains three substances, one of which is the starting adamantanol-1. Molecular ions of the other two according to the mass spectrometry data correspond to adamantyl propylene w / e 176 and adamantyl propanol, m / e 194. The mixture of substances is separated by chromatography on alumina of the second degree of activity. 0.12 g (adamantyl-1) -propena-1 (benzene as eluent), 0.82 g (mp. 80-83 ° C) of 1- (adamantyl-1) -propanol-1 (eluant - a mixture of benzene with diethyl ether in the ratio of 4: 1) and 0.3 g of adamantanol-1 (eluent - ether). Crude 1- (adamantyl-1) -propanol-1 pe crystallized from petroleum ether (so Kip. 38-50 ° C). Yield 1 0.76 g, i.e. 66%, counting on adamantanol-1, which entered into the reaction, and 50% - n., And injected, t. Pl. 85-86 ° C. CP-NMR spectrum: 0.94 (triplet, 3-H, J, 6.5 Hz); 1.32 (singlet, 1-H); 1.06 - 1.43 (complex multiplet, 2-H); 1.51 (broad singlet, 6-H); 1.65 (broad singlet, 6-H); 1.96 (broad singlet, 3-H); 2.81 (quadruplet, 1-H, Js 10 Hz), Js 2.5 Hz,) ppm ; IR spectrum; 3350-3420 cm, (OH). Mass spectrum: b / w 194 (M, 1%); (. „, 3.4%); 165 (M-CsHs, 13.5 135 (M - - CjHeOH, 100%). Found,%: C 80.09: H 11.61. Cis320. Calculated,%: C 80.35; H 11.41. Example 2. The process is carried out with the same quantities of substances as indicated in example 1, but without solvent at 55 ° C. After the completion of the reaction, a dilute soda solution and a 20% potassium hydroxide solution are added to the mixture and boiled for 4 hours. Further processing is similar to that described in Example 1. The yield of 1- (adamantyl-1) -propanol-1 is 65-70%, considering adamantanol reacted. Thus, the proposed method allows easy and good results. .m get a wound It is not easily accessible 1- (adamantyl-1) -propanol-1. The proposed method is much simpler than the known one, since it allows to obtain the target product in one stage, unlike the well-known two-stage process. In addition, it involves the use of more accessible starting compounds (hell .Manthanol-1 and propylene) compared with the initial properties of the known method. Formula of the invention 1. The method of obtaining 1- (adamantyl-1) -propanol-1, different, m, that, in order to simplify the process and increase the yield of the target product, adamantanol-1 exposure ayut reacted with propylene in the presence of trifluoroacetic acid. 2. A method according to claim 1, characterized in that the process is conducted in an environment of a solvent, for example, methylene chloride. Sources of information taken into account when examining: 1.Landa S. et al. Synthesis of some adamantane homologues from adamantanecarboxylic acid, Petrochemistry, No. 8, p. 323, 1968. 2. Stepanov, FN, et al. Synthesis and Reactions of (1-Adamantyl) Acetone, JorH, No. 8, p. 1834, 1972. 3. Lauri F. et al. Adamantane derivatives with choleretic activity, Farmaco Ed. Sclent, No. 22, p. 681, 1967.