RU2309933C1 - Method for preparing adamantyl-containing derivatives of naphthalene - Google Patents

Abstract

FIELD: organic chemistry, adamantine derivatives, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of adamantyl-containing derivatives of naphthalene of the general formula:

, wherein R¹ = R³ means hydrogen atom (H); R² means Ad (1); R¹ means -OH; R² means H; R³ means Ad (2); R¹ means Ad; R² means -OH; R³ means H (3). Method involves adding naphthalene-containing compound chosen from order involving naphthalene, 1-naphthol and 2-naphthol to 1,3-dehydroadamantane in the mole ratio of reagents = 1:(2-4). The addition reaction is carried out in inert solvent medium, for example, diethyl ether or dioxane, at its boiling point (35-100°C) for 30 min in the presence of catalytic amounts of sulfuric acid. Invention allows to develop a method for synthesis of adamantyl-containing naphthalene derivatives for small stages, enhancing the yield of product and decreasing the reaction time.

EFFECT: improved method of synthesis.

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Description

The invention relates to the chemistry of adamantane derivatives, and in particular to a new method for producing adamantyl-containing naphthalene derivatives of the general formula

where R ¹ = R ³ = H, R ² = Ad (1); R ¹ = OH, R ² = H, R ³ = Ad (2); R ¹ = Ad, R ² = OH, R ³ = H (3).

A known method of producing adamantylnaphthalene by the interaction of 1-bromadamantane and lithiumnaphthalene [B. G. Rarog, V. A. Topchiy. ZhORKh, vol. XVII, issue 3, 1981, p. 553-555].

The main disadvantage of this method is the multi-stage process, a large (up to 18 hours) synthesis time. In addition, this method is complicated in preparative terms.

Closest to the proposed invention is a method for producing 2- (adamantyl-1) naphthalene by heating a mixture of 1-bromadamantane with naphthalene in the presence of a catalytic amount of zinc chloride or water [a.c. CCCP 376347, C07C 15/24, publ. 1973].

The main disadvantage of this method is the duration of the reaction (30 hours) and a relatively low (41%) yield.

The objective of the invention is to develop a technologically advanced low-stage method for the synthesis of adamantyl-containing derivatives of naphthalene, which proceeds with a high yield in the initial adamantane.

The technical result is the expansion of the arsenal of chemical derivatives of naphthalene obtained in high yield, simplifying the method of production and isolation, reducing the reaction time.

The technical result is achieved in a new method for producing adamantyl-containing derivatives of naphthalene of the General formula

where R ¹ = R ³ = H, R ² = Ad (1); R ¹ = OH, R ² = H, R ³ = Ad (2); R ¹ = Ad, R ² = OH, R ³ = H (3),

which consists in joining naphthalene-containing compounds to the adamantane derivative, and 1,3-dehydroadamantane is used as an adamantane derivative, and compounds from the series: naphthalene, 1-naphthol, 2-naphthol are used as naphthalene-containing compounds, with molar ratios of reactants equal to 1 :( 2-4), in an inert solvent, for example diethyl ether or dioxane, at a boiling point of 35-100 ° C for 30 minutes in the presence of catalytic amounts of sulfuric acid.

The essence of the method is the catalytic reaction of addition of 1,3-dehydroadamantane to a number of naphthalene-containing compounds:

where R ¹ = R ³ = H, R ² = Ad (1); R ¹ = OH, R ² = H, R ³ = Ad (2); R ¹ = Ad, R ² = OH, R ³ = H (3).

The advantage of this method is a high yield (81-83%), a short reaction time (30 min), ease of isolation of products, and the possibility of obtaining almost any homologues of the naphthalene series, many of which are intermediates for the synthesis of biologically active substances.

The method consists in the interaction of 1,3-dehydroadamantane with naphthalene-containing compounds in an inert solvent, for example in diethyl ether or dioxane, in the presence of a catalyst (sulfuric acid), followed by neutralization of the reaction mass and distillation of the solvent.

The reaction is carried out within 30 minutes By reducing the reaction time, a high yield of the main product is not achieved. The increase in the duration of the reaction is impractical and economically disadvantageous.

It was found that the optimal condition for carrying out the reaction of addition of aromatic compounds to 1,3-dehydroadamantane is its implementation at a molar ratio of 1,3-dehydroadamantane: naphthalene-containing compound 1: 2-4. A smaller excess led to a slight decrease in the yield of the target products. A further increase in the content of the naphthalene derivative did not affect the yield of the target products and was impractical.

The synthesized compounds after distillation of the excess of the starting reagents are sent to the purification step.

The invention is illustrated by the following examples.

Example 1

2- (Adamant-1-yl) naphthalene

The molar ratio of 1,3-dehydroadamantane and naphthalene is 1: 4.

To 15.36 g (0.12 mol) of naphthalene in 10 ml of diethyl ether in the presence of 0.03 g (0.0003 mol) of sulfuric acid in a dry nitrogen atmosphere at room temperature is added dropwise a solution of 4 g (0.0298 mol) of freshly 1 , 3-dehydroadamantane in 20 ml of diethyl ether. The reaction mixture was incubated for 30 min at a temperature of 35 ° C. At the end of the reaction, the mixture is neutralized with sodium carbonate, filtered off, and ether is distilled off. Excess naphthalene is removed by distillation. The product is recrystallized from alcohol.

Yield 6.46 g (82%); so pl. 127-129 ° C.

Found,%: C 91.64; H, 8.36. C ₂₀ H ₂₂ O. Calculated,%: C 91.55; H, 8.45.

PMR spectrum (δ, ppm): 1.54-1.74, 2.05; 7.1-7.7.

Example 2

4- (Adamant-1-yl) -1-naphthol

The molar ratio of 1,3-dehydroadamantane to 1-naphthol is 1: 2.

To 8.64 g (0.06 mol) of 1-naphthol in 10 ml of dioxane in the presence of 0.03 g (0.0003 mol) of sulfuric acid in a dry nitrogen atmosphere at room temperature, a solution of 4 g (0.0298 mol) of freshly boiled 1,3-dehydroadamantane in 20 ml of dioxane. The reaction mixture was incubated for 30 min at a temperature of 100 ° C. At the end of the reaction, dioxane is distilled off. The product is recrystallized from alcohol.

Yield 6.95 g (81%); so pl. 211-212 ° C.

Found,%: C 86.36; H, 7.90. C ₂₀ H ₂₂ O. Calculated,%: C 86.29; H, 7.97.

PMR spectrum (δ, ppm): 1.78-2.1; 5.25; 7.1-7.9.

Example 3

1- (Adamant-1-yl) -2-naphthol

The molar ratio of 1,3-dehydroadamantane and 2-naphthol is 1: 2.

To 8.64 g (0.06 mol) of 2-naphthol in 10 ml of dioxane in the presence of 0.03 g (0.0003 mol) of sulfuric acid in a dry nitrogen atmosphere at room temperature, a solution of 4 g (0.0298 mol) of freshly boiled 1,3-dehydroadamantane in 20 ml of dioxane. The reaction mixture was incubated for 30 min at a temperature of 100 ° C. At the end of the reaction, dioxane is distilled off. The product is recrystallized from alcohol.

Yield 7.12 g (83%); so pl. 194-195 ° C. Found,%: C 86.36; H, 7.90. C ₂₀ H ₂₂ O. Calculated,%: C 86.29; H 7.97; About 5.75.

PMR spectrum (δ, ppm): 1.78-2.1; 4.8; 6.9-7.6.

Thus, the above information indicates the fulfillment of the following set of conditions when using the claimed invention:

- a tool embodying the claimed invention in its implementation, is intended for use in various industries;

- for the claimed invention in the form described in the independent clause of the claims below, the possibility of its implementation using the means and methods described above or known prior to the priority date is confirmed;

- a tool embodying the claimed invention in its implementation is able to ensure the achievement of a technical result.

Therefore, the claimed invention meets the requirement of "industrial applicability".

findings

A new low-stage method for producing adamantyl-containing derivatives of naphthalene has been developed, which allows to obtain compounds of the claimed structural formula with sufficiently high yields. The structure of the obtained compounds was confirmed by PMR spectroscopy and elemental analysis.

Claims (1)

A method of obtaining adamantyl-containing derivatives of naphthalene of the General formula

where R ¹ = R ³ = H, R ² = Ad (1); R ¹ = OH, R ² = H, R ³ = Ad (2); R ¹ = Ad, R ² = OH, R ³ = H (3), consisting in the addition of naphthalene-containing compounds to the adamantane derivative, characterized in that 1,3-dehydroadamantane is used as the adamantane derivative, and compounds of the series: naphthalene, 1-naphthol, 2-naphthol are used at molar ratios of reactants equal to 1 : (2-4), in an inert solvent, such as diethyl ether or dioxane, at a boiling point of 35-100 ° C for 30 minutes in the presence of catalytic amounts of sulfuric acid.