RU2459794C1 - Method of producing diamantane (pentacyclo[7.3.1.14,12.02,7.06,11]tetradecane) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing diamantane (pentacyclo[7,3,1,1^4,12,0^2,7,0^6,11]tetradecane) of formula

(1) through isomerisation of tetrahydrobinor-S. The method is characterised by that the reaction is carried out in the presence of a zeolite Y catalyst in NaH form with ion-exchange degree of 40-60%, first subjected to heat treatment at 450°C for 3-5 hours in air, in amount of 30-70 wt % at reaction temperature 270-300°C for 15-30 hours.

EFFECT: present method uses a cheap catalyst and enables to avoid corrosion and simplifies implementation.

1 cl, 12 ex, 1 tbl

Description

The invention relates to the field of organic chemistry, in particular to a method for producing diamantane (pentacyclo [7.3.1.1 ^4.12 .0 ^2.7 .0 ^6.11 ] tetradecane).

Diamantane (1) is the starting material for the synthesis of heat-resistant synthetic lubricating oils or their components, and, taking into account their good heat-insulating properties and low viscosity index, as cable oil; used to obtain medicines, high molecular weight (polymer) materials, solvent-resistant rubbers (EI Bagriy. Adamantany. M: Nauka, 1989, 256 pp. [1]; S. Hala, M. Kuras, P. Zachar. Sb. VSCHT Praze DS v. 33, p.305-321 (1976), RJChem. 1977, 13P337 [2]; RCFort. Adamantane: The chemistry of diamond molecules. NY; Dekker, 1976, 385 p. [ 3]; MAMcKervey. Tetrahedron, V. 36, p. 971-992 (1980) [4]).

Diamantane (1) is obtained by skeletal isomerization of thermodynamically less stable pentacyclic C ₁₄ H ₂₀ hydrocarbons, in particular, it was synthesized by isomerization of a norbornene dimer - pentacyclo [8.2.1.1 ^4.7 0. ^2.9 .0 ^3.8 ] tetradecan according to the scheme

The low yield of diamantane (1%) is due to the destruction of one of the cycles, which is confirmed by the formation of a by-product of the tetracyclic hydrocarbon 1,2-butanoadamantane (3) with a yield of 40% (CACupas, PRSchleyer, DJTrecker. J. Amer. Chem. Soc , V.87, p.917-918 (1965) [5]).

Three stereoisomers of a pentacyclic hydrocarbon are known (2). Isomerization of the least stressed exo-trans-exo-isomer (2a) leads to the best results.

So, during the isomerization of compound (2a) under the action of an AlBr ₃ catalyst, the yield of diamantane (1) was 11%. The main reaction product is 1,2-tetramethylene adamantane (3). The most strained endo-trans-exo-isomer (26) under these conditions selectively turns into compound (3) (VZWilliams, PvRSchleyer, GJGleicher, LBRodewald. J. Amer. Chem. Soc., V.88, p. 3862 (1966) [6]).

The disadvantages of the methods:

1. Low yield of target diamantane (1).

2. Non-selectivity of the process and the formation of a difficult to separate mixture of products.

The yield of diamantane (1) depends critically on the structure of the initial hydrocarbon, the nature of the catalyst, and the reaction conditions. A number of polycyclic bridging hydrocarbons of the composition C ₁₄ H ₂₀ obtained on the basis of norbornene by the Diels-Alder reaction with various cyclic dienes are also able to rearrange into diamantane (1).

Hydrocarbons (4) and (5) upon contact with AlBr ₃ form diamantane with a yield of 20-25% (TMGund, E. Osawa, VZWilliams, PvRSchleyer. J. Org. Chem., V.39, No. 20, p.2979- 2987 (1974) [7]).

Isomerization of (6) and (7) in the presence of AlBr ₃ in tert-butyl bromide medium leads to diamantane (1) with a yield of 44 and 34%, respectively.

The disadvantages of the methods:

1. The inaccessibility and multi-stage synthesis of the source hydrocarbons.

2. Low yield of the target product.

3. Difficulties in the isolation of diamantane (1) due to the formation of by-products.

The most suitable for the preparative preparation of diamantane (1) is the (4 + 4) -dimer of norbornadiene - heptacyclo [8.4.0.0 ^2.12 .0 ^3.8 .0 ^4.6 .0 ^5.9 .0 ^11.13 ] tetradecane ( 10), the trivial name of which is “binor-S” (TMGund, E. Osawa, VZWilliams, PvRSchleyer. Tetrahedron Lett., No. 44, p. 3877-3880 (1970) [8]; PvRSchleyer. Hexacyclotetradecanes. Pat. USA, No. 3673268 (06/27/1972), CL 260-666 RU, (C07С 13/28) [9]):

Hydrogenation of binor-S (10) at 200 ° C and 305 atm H ₂ in the presence of a Pt catalyst or PtO ₂ in ice-cold CH ₃ COOH leads to the opening of cyclopropane rings and the formation of tetrahydrobinor-S (11) in almost quantitative yield.

Tetrahydrobinor-S (11) is slowly added dropwise to CS ₂ or a cyclohexane solution of well-dried AlBr ₃ (25% by weight of C ₁₄ H ₂₀ ). The reaction is exothermic. After adding the entire amount of compound (11), the mixture is boiled for 0.5-1 hours. The yield of diamantane (1) is 65%.

The disadvantages of the method:

1. Moderate yield of the target product.

2. The formation of by-products makes it difficult to isolate diamantane (1).

3. The use of a significant amount of catalyst (25%).

4. Use as a solvent of toxic explosive carbon disulfide.

In the presence of superacid catalysts: B (OSO ₂ CF ₃ ) ₃ (A), CF ₃ SO ₃ H-SbF ₅ (1: 1) (B), CF ₃ SO ₃ HB (OSO ₂ CF ₃ ) ₃ (1: 1 ) (B) - from tetrahydrobinor-S (11), diamantane (1) is obtained in high yields (O. Farooq, SMFFarnia, M. Stephenson, GAOlah. J. Org. Chem., V.53, No. 12, p. 2840 -2843 (1988) [10]):

When processing the reaction mixture with ultrasound, the reaction time is reduced to 1.75 hours

The disadvantages of the method:

1. The inaccessibility of superacid catalysts.

2. The use of stoichiometric amounts of superacids complicates the isolation of the target product.

3. When neutralizing the reaction mixture, a large amount of waste and wastewater is generated.

4. The need to use low temperatures (0 ° C).

To a well-mixed heterogeneous mixture of binor-S (7.6 mmol) and NaBH ₄ (22.8 mmol) (under argon or nitrogen) in dry Freon-113 (40 ml) at -30 ° C, 12 ml of CF ₃ SO ₃ are added over 30 minutes H (137 mmol) in a stream of dry Ar or N ₂ . During the addition of acid due to the exothermic nature of the reaction, the mixture is cooled to -78 ° C, the mixture is then kept at room temperature for 3-5 hours. The yield of diamantane (1) by this method reaches 99% (GAOlah, A.Wu, O. Farooq, GKSPrakash. J. Org. Chem., V.54, No. 6, p.1450-1451 (1989) [11]) .

The disadvantages of the method:

1. The inaccessibility and high cost of the reagents (NaBH ₄ , CF ₃ SO ₃ H).

2. The need for a reaction in a stream of dry argon or nitrogen due to the use of fire and explosive sodium borohydride.

3. The need to cool the mixture to -78 ° C (exothermic reaction).

Upon hydrogenation (hydrogen pressure 1 atm) of a norbornadiene dimer (12) (“Katz dimer”) in acetic acid in the presence of an Adams catalyst after hydrogenolysis of the cyclopropane ring and reduction of the olefinic bond, a tetrahydro derivative (13) of an unknown structure is formed. During gas-phase isomerization of hydrocarbon (13) using a heterogeneous catalyst - platinum supported on chlorinated Al ₂ O ₃ , diamantane (1) was obtained (T. Courtney, DE Johnston, M. A. McKervey, JJ Rooney. J. Chem. Soc, Perkin Trans. I, No. 21, p. 2691-2696 (1972) [12]):

The isomerization of tetrahydrobinor-S (11) in the gas phase at 150 ° C in an HCl atmosphere over the chlorinated catalyst Pt-Al ₂ O ₃ leads to the formation of diamantane (1).

Based on the similarity in three characteristics (the initial reagent is tetrahydrobinor-S, a heterogeneous catalyst, the formation of diamantane as a result of the reaction (1)), the prototype is taken using the isomerization of tetrahydrobinor-S using a heterogeneous catalyst of platinum supported on chlorinated Al ₂ O ₃ [12] .

The prototype has the following disadvantages:

1. The use of an expensive platinum catalyst.

2. Corrosion of equipment due to the use of HCl in the catalyst.

The objective of the present invention is to simplify and cheapen the technology for producing diamantane (1).

The authors propose a method for producing diamantane (1), which does not have these drawbacks.

The essence of the method consists in the isomerization of tetrahydrobinor-S (11) in the presence of a zeolite Y catalyst in NaH form with a degree of ion exchange of 40-60%, previously subjected to heat treatment at 450 ° C for 3-5 hours in an atmosphere of air, in an amount of 30- 70 wt.% At a reaction temperature of 270-300 ° C for 15-30 hours.

Under optimal conditions, at 70% conversion of tetrahydrobinor-S (11), the only reaction product is diamantane (1).

Significant differences of the proposed method from the prototype:

1. To obtain diamantane (1) from tetrahydrobinor-S (11), a heterogeneous zeolite Y catalyst in NaH form with an ion exchange degree of 40-60%, previously subjected to heat treatment at 450 ° C, is used.

The advantages of the proposed method.

1. The availability of the catalyst (zeolite Y in NaH form is produced by Salavatnefteorgsintez JSC).

2. The absence of corrosion and simplicity of hardware design.

The proposed method is illustrated by examples.

General technique.

30-70 wt.% Zeolite Y in NaH form with a degree of ion exchange of 40-60%, previously subjected to heat treatment at 450 ° C, tetrahydrobinor-S, cyclohexane as a solvent was placed in a glass ampoule, the ampoule was sealed, placed in a micro autoclave, hermetically sealed closed and heated for 15-30 hours at 270-300 ° C. After the reaction, the autoclave (ampoule) was cooled to room temperature, opened, after filtering off the catalyst, the solvent was distilled off, the residue was crystallized from hexane. The yield of diamantane (1) was 50-70%.

EXAMPLE 1. In a glass ampoule (V = 20 ml), 5 mmol of tetrahydrobinor-S, 0.66 g of zeolite Y in NaH form with a degree of ion exchange of 40%, previously subjected to heat treatment at 450 ° C, 2 ml of cyclohexane were placed, the ampoule was sealed, placed in a micro autoclave, hermetically closed and heated at 300 ° C for 30 hours. After the reaction, the autoclave (ampoule) was cooled to room temperature, opened, after filtering the catalyst, removing the solvent and crystallizing the residue from hexane, diamantane (1) was isolated in 70% yield.

The resulting diamantane (1) had so pl. 244-245 ° C (hexane). Infrared spectrum (υ, cm ^-1 ): 2926, 2907, 2880, 2850, 1445, 1305, 1230, 1179, 1072, 1039, 980. ¹³ C NMR spectrum (CDCl ₃ , δ, ppm): 37.76 (C ¹ , C ² , C ⁶ , C ⁷ , C ¹¹ , C ¹² ), 38.51 (C ³ , C ⁵ , C ⁸ , C ¹⁰ , C ¹³ , C ¹⁴ ), 26.18 (C ⁴ , C ⁹ ). Mass spectrum, m / z (J rel.,%): 188 [M] + (100), 160 (5), 159 (10), 145 (8), 131 (13), 130 (18), 120 (7), 105 (15), 91 (28), 79 (25), 67 (15). Found,%: C 88.75, H 11.25. C ₁₄ H ₂₀ . Calculated,%: C 88.29, H 10.71.

Other examples confirming the method are given in table 1.

Table 1 The results of experiments on the synthesis of diamantane (1) from tetrahydrobinor-S (11) in the presence of a zeolite Y catalyst in NaH form with a degree of ion exchange of 40%, previously subjected to heat treatment at 450 ° C in air №№ Amount of catalyst, wt.% Temperature ° C Reaction time, h The conversion of tetrahydrobinor-S (11),% The output of diamantane (1),% one 2 3 four 5 6 one thirty 270 fifteen 23 23 2 thirty 270 twenty 37 36 3 thirty 270 thirty 39 38.5 four fifty 270 fifteen 24 24 5 fifty 200 twenty 40 39 6 fifty 270 thirty 65 60 7 70 270 fifteen 50.6 45 8 70 270 twenty 55 53 9 fifty 300 thirty 72 70 10 70 300 twenty 68 67 eleven 70 300 thirty 51 42 12* fifty 270 twenty 75 72 * - zeolite Y in NaH form with a degree of ion exchange of 60%

Claims (1)

The method of producing diamantane (pentacyclo [7.3.1.1 ^4.12 .0 ^2.7 .0 ^6.11 ] tetradecane) of the formula (1)

isomerization of tetrahydrobinor-S, characterized in that the reaction is carried out in the presence of a zeolite Y catalyst in NaH form with a degree of ion exchange of 40-60%, previously subjected to heat treatment at 450 ° C for 3-5 hours in an atmosphere of air, in an amount of 30- 70 wt.% At a reaction temperature of 270-300 ° C for 15-30 hours