Method of obtaining adamantyl containing derivatives of 1,4-diketones

FIELD: chemistry.

SUBSTANCE: invention relates to the method of obtaining new adamantly containing derivatives of symmetric 1,4-diketones with the general formula: where R1=H or CH3, R1-H or CH3, which are potentially biologically active materials. The method consists of connecting to 1,3-dehydroadamantan or 5,7-dimethyl-1,3-dehydroadamantan symmetrical 1,4-diketone: 2,5-hexanedione or 1,4-cyclohexanedione with their molar relation equal to 1:1 at the temperature of 80°C for a period of 5 hours.

EFFECT: it makes it possible to obtain new compounds with a high output.

4 ex

 

The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining adamantylidene symmetric derivatives of 1,4-diketones of General formula:

where R1=N or CH3,

R1=N or CH3,

which are potentially biologically active substances.

A method of obtaining adamantylidene β-diketones [RF Patent №2187493 SS 49/15, 49/792, 45/45, 45/61, 07D 307/46, 333/16. Publ. BI No. 23, 2002], consisting in the interaction of 1,3-dehydroalanine with some β-diketones.

However, this method does not lead to obtaining substances claimed structural formulas. In addition, γ-diketones unlike β-diketones are not strong CH-acids have several reaction centers and the formation of substances claimed structural formulas for interaction γ-diketones with 1,3-dehydroalanine and 5,7-dimethyl-1,3-dehydroalanine is not obvious.

A method of obtaining adamantylidene γ-diketones, for example 1,4-di-(1-substituted)butane-1,4-dione interaction (1-adamantylamine)malonate with sodium [Stetter H., Rauscer E. // Chem. Ber. 1960. Bd. 93. No. 9. S.2054-2057].

A significant disadvantage of this method is, first of all, a multi-stage, low you the od of target products and receive diazepamtradenames connection.

The task of the invention is to develop a technologically advanced one-step method of synthesis adamantylidene symmetric derivatives of 1,4-diketones proceeding with a high output.

The technical result is an expanding Arsenal of chemical compounds obtained in high yield in a new way.

The technical result is achieved in a new method of obtaining adamantylidene symmetric derivatives of 1,4-diketones of General formula:

where R1=N or CH3,

R1=N or CH3,

which consists in joining the adamantane derivative of the corresponding symmetrical 1,4-diketone, and as adamantane derivative used 1,3-dehydroalanine or 5,7-dimethyl-1,3-dehydroalanine, and as a source of symmetrical 1,4-diketones are used 2.5-hexanedione or 1,4-cyclohexanediol, and the process performed when a molar ratio of 1:1 at a temperature of 80°C for 5 hours.

The essence of the method is the reaction of joining 1,3-dehydroalanine (1,3-DCA) and 5,7-dimethyl derivative (5,7-DM-1,3-DCA) symmetric 1,4-diketones:

where R1=H or CH3.

High nucleophiles the ü 1,3-dehydroalanine and 5,7-dimethyl derivative allows to obtain products attach data symmetric 1,4-diketones with high yields in a fairly mild conditions in one stage.

The advantage of this method is the high output (≈80%), as well as the possibility of obtaining almost any homologues of this series, which are also potentially biologically active substances.

In the interaction of 1,3-DCA or 5,7-DM-1,3-DCA with 2.5-hexanedione or 1,4-cyclohexandione the only direction the reaction is s-adamantylamine α-carbon atom source γ-diketone. Moreover, the interaction of 1,3-DCA or 5,7-DM-1,3-DCA with 1,4-cyclohexanediol due to its full symmetry is formed on one target product. In the interaction of 1,3-DCA or 5,7-DM-1,3-DCA with 2.5-hexanedione is formed on one of the target product - CH2group, the number of products attachment of CH3the group is small, because of thermodynamic stability of the formed secondary radicals. Products O-adamantylamine absent because of a low degree enolizatsii source γ-diketones.

As studies have shown that the reaction is sensitive to temperature. Found that reducing the reaction temperature from 80 to 35-40°output decreases as the holding of interaction in the environment of boiling diethyl ether led to obtain the desired reaction products. Further increase in temperature (>80° (C) leads to a decrease in the output of the target product, that seems to be associated with the occurrence of adverse reactions recombination adamantyl radicals.

Suitable molar ratio of the reagents 1,3-DCA (or 5,7-dimethyl-1,3-DCA): symmetric 1,4-diketone is 1:1, since it is a high yield of the target compounds.

Reducing the duration of the reaction less than 5 hours ceteris paribus leads to a slight decrease in the yield of the target products. The increased duration of the reaction over 5 hours does not significantly change the yield of the target products.

The method is as follows.

To equimolar quantity of symmetrical 1,4-diketone is poured a solution of 1,3-dehydroalanine (or 5,7-dimethyl-1,3-dehydroalanine) in absolute diethyl ether. The ether is distilled off and the mixture of 1,3-dehydroalanine (or 5,7-dimethyl-1,3-dehydroalanine) and symmetric 1,4-diketone heated for 5 hours at a temperature of 80°C. the Synthesized adamantylidene derivatives of symmetrical 1,4-diketones are directed at the purification stage. The yield of the target products is 80%.

The invention is illustrated by the following examples.

Example 1

Synthesis of 3-(1-substituted)hexane-2,5-dione.

To 1,1414 g (0.01 mol) of 2,5-hexanedione in a dry nitrogen atmosphere at room temperature pin solution of 1.34 g (0.01 of the ol) svezheosazhdennoi 1,3-DCA in 20 ml of absolute diethyl ether.

The solvent is distilled off, and then bring the temperature of the reaction mass up to 80°With stand without stirring for 5 hours. Upon completion of the reaction mass vaccum and get 1,99 g (0,008 mol, 80%) of 3-(1-substituted)hexane-2,5-dione, representing colorless crystals with TPL=70-73°C.

Mass spectrum, m/e: 248(5%)M+, 205 (5%) [M-CH3WITH]+, 135(100%) Ad+.

Example 2

Synthesis of 3-(3,5-dimethyl-1-substituted)hexane-2,5-dione.

Similarly, from 1,1414 g (0.01 mol) of 2,5-hexanedione and of 1.62 g (0.01 mol) svezheosazhdennoi 5,7-DM-1,3-DCA obtain 2.2 g (0,008 mol, 80%) of 3-(3,5-dimethyl-1-substituted)hexane-2,5-dione, representing viscous liquid with TKip=210°C/20 mm Hg

Mass spectrum, m/e: 276(3%)M+, 233 (3%) [M-CH3WITH]+, 163 (100%) (SN3)2Ad+.

Example 3

Synthesis of 2-(1-substituted)cyclohexane-1,4-dione

Similarly, from 1,1213 g (0.01 mol) of 1,4-cyclohexandione and 1.34 g (0.01 mol) svezheosazhdennoi 1,3-DCA gain of 1.97 g (0,008 mol, 80%) of 2-(1-substituted)cyclohexane-1,4-dione, representing colorless crystals with TPL=125-128°C.

Mass spectrum, m/e: 246 (1%) M+, 135 (100%) Ad+.

Example 4

Synthesis of 2-(3,5-dimethyl-1-substituted)cyclohexane-1,4-dione

Similarly, from 1,1213 g (0.01 mol) of 1,4-cyclohexan is it of 1.62 g (0.01 mol) svezheosazhdennoi 5,7-DM-1,3-DGA get 2,19 g (0,008 mol, 80%) of 2-(3,5-dimethyl-1-substituted)cyclohexane-1,4-dione, representing colorless crystals with TPL=68-70°C.

Mass spectrum, m/e: 274 (1%) M+, 163 (100%) (CH3)2Ad+.

The method of obtaining adamantylidene symmetric derivatives of 1,4-diketones of General formula

,

where R1- N or CH3, R2-

R1- N or CH3, R2-

which consists in joining the adamantane derivative of the corresponding symmetrical 1,4-diketone, and as adamantane derivative used 1,3-dehydroalanine or 5,7-dimethyl-1,3-dehydroalanine, and as a source of symmetrical 1,4-diketones are used 2.5-hexanedione or 1,4-cyclohexanediol, and the process performed when a molar ratio of 1:1 at a temperature of 80°C for 5 hours



 

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