RU2559356C1 - Method of producing 5(6)-nitro-1-(4-nitrophenyl)-1,3,3-trimethylindanes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 5- and 6-nitro-1-(4-nitrophenyl)-1,3,3-trimethylindanes by reacting 1,1,3-trimethyl-3-phenylindane with nitric acid. According to the disclosed method, nitration of 1,1,3-trimethyl-3-phenylindane is carried out in the presence of a catalyst in the form of amorphous mesoporous aluminosilicate. The reaction is carried out at 100-130°C with molar ratio phenylindane:HNO₃=1:6-14 for 8 hours in the presence of 2-4 wt % (with respect to the reaction mixture) catalyst.

EFFECT: method avoids the use of sulphuric acid during nitration, simplifies and lowers the cost of the process.

1 dwg, 1 tbl, 10 ex

Description

The invention relates to the field of organic chemistry, in particular to a method for producing 5- and 6-nitro-1- (4-nitrophenyl) -1,3,3-trimethylindanes or dinitrophenylindanes.

Dinitrophenylindanes are used as starting compounds in the synthesis of 5- and 6-amino-1- (4-aminophenyl) -1,3,3-trimethylindanes, which serve as monomers for the production of polyimide materials used in gas separation membranes [1. Isaac V. Farr. Synthesis and characterization of novel polyimide gas separation membrane material systems. Blacksburg, Virginia, July 26, 1999].

The industrial methods for producing nitroaromatic compounds are based on the reaction of liquid-phase nitration of arenes and their derivatives with a mixture of concentrated HNO ₃ and H ₂ SO ₄ . The nitration mixture used in industrial nitration processes contains about 30% HNO ₃ , 60% H ₂ SO ₄ and 10% H ₂ O [2. Gorelik M.V., Efros L.S. Fundamentals of chemistry and technology of aromatic compounds. M.: Chemistry, 1992. 640 p.].

The process is carried out until the concentration of H ₂ SO ₄ is reduced to the limit value, after which the process is stopped, since with a greater dilution of sulfuric acid, the process is less efficient.

An obligatory stage of liquid-phase nitration with a nitrating mixture is the regeneration of spent H ₂ SO ₄ . For the regeneration of spent H ₂ SO ₄ , which, in addition to water, also contains nitrogen compounds and organic substances, special equipment and high energy consumption are required. In addition, the formation of large volumes of wastewater containing dilute H ₂ SO ₄ , as well as dissolved nitrogen oxides and phenolic impurities, poses a serious threat to the environment. The need for H ₂ SO ₄ regeneration and disposal of large amounts of sulfuric acid waste is the main disadvantage of liquid-phase nitration [3. Sheldon RA, Downing RS // Appl. Catal., A: General, 1999, v. 189, p. 163-183].

All this stimulates the search for alternative nitration methods that would dramatically reduce or even completely eliminate the use of H ₂ SO ₄ in nitration processes. One solution to this problem is nitration on heterogeneous catalysts.

The literature describes methods for gas and liquid phase nitration of benzene, toluene, xylenes and naphthalene on heterogeneous catalysts.

This method has undoubted advantages, since does not require the use of sulfuric acid, and, therefore, eliminates the need for its regeneration for subsequent return to the process. In the literature [4-21], the catalysts used in the process of nitration of benzene and toluene are very widely represented. If we proceed from the nature of the catalytic effect, the characteristics of the composition and structure, then all the catalysts proposed for the nitration of aromatic hydrocarbons can be divided into three groups.

The first group includes catalysts, which are various solid carriers impregnated with inorganic acids. This type of catalyst can be considered as a modification of the liquid-phase process, aimed at reducing the amount of H ₂ SO ₄ due to its deposition on a solid carrier. Such catalytic systems are described in detail in [4. US Patent 5,030,776, 1991 .; 5. Smith A.S., Narvaez LD, Akins BG ea Synth. Commun., V.29, No. 23, p.4187-4192].

For nitration of benzene is proposed [6. US Patent 3928476, 1975] use Al ₂ O ₃ and some aluminosilicates coated with H ₂ SO ₄ or H ₃ PO ₄ . Similar catalytic systems are also described in [7. Kogelbauer A., Vassena D., Prince R., Armor JN // Catal. Today, v. 55, p. 151-160; 8. Riego JM, Sedin Z., Zaldivar JM ea // Tetrahedron Lett., 1996, v. 37, No. 4, p. 513-516].

The carrier is impregnated with H ₂ SO ₄ , followed by evacuation and drying at 130 ° C. The finished catalyst contains up to 70% H ₂ SO ₄ . Nitration is carried out at 25 ° C in a solution of CH ₂ Cl ₂ , the nitrating agent is 70-90% HNO ₃ . Under the selected conditions, benzene and toluene are converted to the corresponding nitro compounds with a yield of 98-100%; such high yields of products are achieved in no more than 1 hour. The process is highly selective

A known variant of nitration of toluene HNO ₃ in the vapor phase at 80-180 ° C and reduced pressure [9. US Patent 4112006, 1978]. Here, the catalysts are SiO ₂ or Al ₂ O ₃ impregnated with H ₂ SO ₄ or H ₃ PO ₄ and also containing additives of salts of these acids. The yield of nitrotoluene is 76.6%, and the ratio of steam-nitrotoluene: ortho-nitrotoluene reaches 1.84. The nitration rate of substituted arenes (toluene, xylenes) can be increased by introducing a small amount of anhydrous CaSO ₄ or CaO into the system.

For vapor-phase nitration of benzene with nitrogen dioxide, silica gel impregnated with benzenesulfonic acid is used (170 ° C, the yield of nitrobenzene is 15-11%) [10. Jap. Patent 1-213256, 1989].

However, these catalysts are not yet suitable for large-scale use. One of the reasons is the low stability of the used catalytic systems, which the authors explain by leaching of sulfuric acid from the surface of the carrier, as a result of which even the best catalysts lose activity during operation.

The second group includes catalysts based on various oxide systems. Many of these contacts contain transition metal oxides of groups IV-VI of the periodic system.

As a catalyst for the vapor-phase nitration of aromatic hydrocarbons with nitrogen dioxide (150-225 ° C) in the patent [11. US Patent 4347389, 1982] proposes the use of an oxide phosphonovanadium system. The atomic ratio of phosphorus and vanadium in the catalyst varies over a fairly wide range, from 1: 2 to 2: 1. When nitrating toluene with this catalyst, it is possible to obtain the ratio para-nitrotoluene: otro-nitrotoluene = 1: 2.

In the work [12. Sato N., Hirose K., Nagai K. e. A. // Appl. Catal., A: Chemical, v. 175, p.201-207. 13. Sato H., Hirose K. // Appl. Catal., A: Chemical, 1998, v. 174, p. 77-81. 14. US Patent 4551568, 1985. 15. US Patent 5004846, 1991] a series of binary systems were tested as catalysts for the vapor-phase nitration of benzene with nitric acid: TiO ₂ -WO ₃ , TiO ₂ -MO ₃ , TiO ₂ -ZnO, TiO ₂ - ZrO ₂ , TiO ₂ -Al ₂ O ₃ , TiO ₂ -SnO ₂ , ZrO-WO ₃ . Of all the catalysts, the contacts showed the highest activity, in which the main components are TO ₂ or ZrO ₂ oxides, in particular, such as TiO ₂ -WO ₃ , ZrO ₂ -WO ₃ , TiO ₂ -MoO ₃ , TO ₂ -ZnO. They succeeded in obtaining a conversion 64,3-82,7% HNO ₃ (at 160 ° C), whereas in catalysts ₂ -ZrO ₂ TO, TO ₂ -Al ₂ O _3, TO ₂ -SnO ₂ HNO conversion did not exceed ₃ 51% The authors attribute the difference in the activity of the catalysts to the difference in their acidity.

, $$S{O}_4^{2-}/Ti{O}_2\left(75\%\right)-W{O}_3\left(25\%\right)$$

и $$S{O}_4^{2-}/Ti{O}_2$$

проявляли более высокую нитрующую активность (по сравнению с несульфатированными образцами). Данный эффект, по мнению авторов, объясняется увеличением бренстедовской кислотности. Среди изученных катализаторов наилучшим оказался образец $$S{O}_4^{2-}/Ti{O}_2\left(80\%\right)-Mo{O}_3\left(20\%\right)$$

, выход нитробензола на котором составил 87%, производительность составляла 0,72 кг/кг·ч.In the work [16. Sato N., Nagai K, Yoshioka., Nagaoka // Appl. Catal., A: Chemical, 1998, v.175, p.209-213], sulfated metal oxides are highly active in vapor-phase nitration of benzene with nitric acid (67%). They were prepared by treating the corresponding oxides with sulfuric acid, followed by calcination at 500 ° C. The catalysts thus obtained $$S{O}_{\mathrm{four}}^{2-}/Ti{O}_2\left(80\%\right)-Mo{O}_3\left(\mathrm{twenty}\%\right)$$

, $$S{O}_{\mathrm{four}}^{2-}/Ti{O}_2\left(75\%\right)-W{O}_3\left(25\%\right)$$

and $$S{O}_{\mathrm{four}}^{2-}/Ti{O}_2$$

showed higher nitrating activity (compared with non-sulfated samples). This effect, according to the authors, is explained by an increase in Brandsted acidity. Among the studied catalysts, the sample turned out to be the best $$S{O}_{\mathrm{four}}^{2-}/Ti{O}_2\left(80\%\right)-Mo{O}_3\left(\mathrm{twenty}\%\right)$$

the yield of nitrobenzene on which was 87%, the productivity was 0.72 kg / kg · h.

A common disadvantage of mixed transition metal oxides is the high cost and complexity of preparation, as well as the difficulty of regulating the porous structure.

The third group consists of catalysts based on various zeolites and aluminosilicates, natural and synthetic [17. US Patent 4,754,083, 1988]. In this case, we are most often talking about gas-phase nitration of arenas, where nitric oxides, in particular NO ₂ , act as nitrating substances. Moreover, zeolites such as H-mordenite, HY, H-ZSM-5 and H-erionite have been investigated even in gas-phase nitration of nitrobenzene. True, they showed relatively low activity and low stability, and the duration of their continuous operation was measured for several hours.

Highly effective catalysts for the vapor-phase nitration of benzene with diluted HNO ₃ are obtained from modified zeolites Y [18. Bertea LE, Kouwenhoven HW, Prins R. // Studies in Surface Science and Catalysis., 1993, v. 78, p. 607-614] and mordenite [19. Bertea LE, Kouwenhoven HW, Prins R. // Appl. Catal., A: Chemical, 1995, v. 129, p. 299-250]. The latter allows you to get nitrobenzene at 170 ° C with a yield of up to 80-85% and a productivity of 0.6 g / g · h with stable operation for 120 hours

The most active and stable in vapor-phase nitration of benzene was a catalyst based on the natural clinoptilolite zeolite [20. Bertea L.E., Kouwenhoven H.W., Prins R. // Stud. Surf Sci. Catal., 1994, v. 84, p. 1973-1980]. On it, the nitrobenzene productivity was 0.65 g / g · h.

Japanese researchers [21. Sato N., Hirose K., Nagai K. e.a. // Appl. Catal., A: Chemical, 1998, v. 175, p.201-207 .; 22. EP 0343048 A1, B1, 1993 .; 23. Sato H., Hirose K. // Appl. Catal., A: Chemical, 1998, v.174, p.77-81] studied the vapor-phase nitration of benzene with diluted HNO ₃ on catalysts prepared from montmorillonite. It turned out that the catalytic activity of the starting H-montmorillonite is relatively small, but after ion exchange of H-montmorillonite with multivalent metal cations (groups IIA-IIIA and IB-IVB of the periodic table), its activity sharply increased, while the acidity of montmorillonite also increased. The degree of increase in nitrating activity of the catalyst depends on the type of cation introduced into it. The highest conversion of HNO ₃ (93.4%) is achieved on A1-montmorillonite (160 ° C): selectivity for nitrobenzene is 97.8%, and the productivity of the catalyst is 3.65 g / g · h.

A significant drawback for zeolites and modified clays is the presence of microporosity, which makes it impossible to use them for catalytic conversions of bulk molecules with a diameter d≥0.1 nm.

The synthesis of 5- and 6-nitro-1- (4-nitrophenyl) -1,3,3-trimethylindanes in the presence of heterogeneous catalysts, including zeolites and amorphous aluminosilicates, is not described in the literature.

Known methods for producing 5- and 6-nitro-1- (4-nitrophenyl) -1,3,3-trimethylindanes [24. US Patent 1,470,705, 1974; 25. US Patent 3,856,752, 1974; 26. US Patent 3983092, 1976; 27. US Patent 1492511, 1976] provide for liquid phase nitration of 1,1,3-trimethyl-3-phenylindane (phenylindane) with a nitrating mixture. As indicated in the patent [26. US Patent 3983092, 1976], the nitrating mixture contains about 25% HNO ₃ and 75% H ₂ SO ₄ , while the molar ratio phenylindane: HNO ₃ is 1: 8. The process is carried out at 5 ° C for 4 hours. The yield of dinitrophenylindanes is ~ 70%. During the reaction, nitric acid is completely or partially consumed, and the water formed must be separated in one way or another from sulfuric acid, which serves as a catalyst and medium, in order to return it to the nitration process. The “acid circulation” that arises in this way causes significant hardware, technology, economic and environmental disadvantages of the liquid-phase method of phenylindane nitration.

The objective of the present invention is to develop a more efficient method for producing dinitrophenylindanes based on the use of a heterogeneous catalyst, which eliminates the use of sulfuric acid and avoids a significant part of the disadvantages of the nitration process.

The solution to this problem is achieved by the fact that the method of producing 5- and 6-nitro-1- (4-nitrophenyl) -1,3,3-trimethylindanes is carried out, according to the invention, by nitration of 1,1,3-trimethyl-3-phenylindane in the presence of amorphous mesoporous aluminosilicate at 100-130 ° C at a molar ratio of phenylindane: HNO ₃ = 1: 6 ÷ 14, for 8 hours, in the presence of 2-4 wt.% (calculated on the reaction mixture) of the catalyst.

A comparative analysis of the proposed solution with the prototype shows that the claimed method differs from the prototype in that in the synthesis of dinitrophenylindanes instead of sulfuric acid, a heterogeneous catalyst is used, which is a mesoporous aluminosilicate. The process is carried out at 100-130 ° C, with a molar ratio of phenylindane: HNO ₃ = 1: 6 ÷ 14, for 8 hours, in the presence of 2-4 wt.% (Calculated on the reaction mixture) of the catalyst. Phenylindane conversion reaches 100%, dinitrophenylindane yield - 50-95%. After completion of the reaction, the catalyst was separated by filtration. It can be used repeatedly.

The reaction can be carried out both in solvents (dichlorobenzene, alkanes) and without them.

The reaction proceeds according to the scheme:

The mesoporous aluminosilicate used in the invention is an amorphous aluminosilicate material with a developed porous structure. Mesoporous aluminosilicate was synthesized by mixing oligomeric esters of orthosilicic acid with a water-alcohol solution of Al (NO ₃ ) · 9H ₂ O at 20-25 ° C for 25-30 minutes, followed by heating to 60 ° C with stirring. The resulting gel was treated with an ammonia solution, dried in air at 150 ° C for 8 h, then calcined in a muffle furnace at 650 ° C for 5 h. The calcined amorphous mesoporous aluminosilicate was ground to a powder with a fractional composition <100 μm. The porous structure of amorphous aluminosilicate is characterized by the presence of mesopores having a wide distribution of pore volume size (in the range of 2-5 nm, Fig. 1). The specific surface area of the mesoporous aluminosilicate according to BET is 550 m ² / g, the specific pore volume is 0.9 cm ³ / g. The molar ratio of SiO ₂ / Al ₂ O ₃ is 20. The total acidity measured by thermally programmed desorption of ammonia is 550 μmol / g.

The proposed method is as follows.

Phenylindane nitration is carried out in a batch isothermal reactor at a temperature of 100-130 ° C, atmospheric pressure, in the presence of 2-4 wt.% (Calculated on the reaction mixture) of the catalyst. The molar ratio of phenylindane: nitric acid is 1: 6 ÷ 14. For experiments, 67% nitric acid is used, the purity of phenylindane is 99.8%, and dichlorobenzene is used as the solvent. The initial concentration of phenylindane in the reaction mass is 0.44 mol / L. At the end of the synthesis, the reaction mass is filtered off from the catalyst and washed from excess nitric acid. Unreacted phenylindane and mononitrophenylindanes are isolated from the reaction mass by distillation under reduced pressure. The remainder, dinitrophenylindanes, was recrystallized from CCl ₄ .

Quantitative analysis of the reaction mass is carried out by gas-liquid chromatography on an HRGS 5300 Mega Series Carlo Erba instrument with a flame ionization detector; analysis conditions: 25 m glass capillary column, SE-30 phase, temperature programming 50-280 ° C (8 ° C / min), detector temperature 250 ° C, evaporator temperature 300 ° C, carrier gas-helium - 30 ml / min

Product identification is carried out by NMR and high resolution mass spectrometry.

NMR spectra were recorded on a Bruker AVANCE-400 spectrometer with operating frequencies of 400.13 ( ¹ H) and 100.62 MHz ( ¹³ C) in CDCl ₃ .

High resolution mass spectra were obtained on a Fisons Trio 1000 instrument with a DB-5 capillary column; temperature programming from: 50 to 320 ° C at a speed of 4 ° C / min; 70 eV.

The proposed method is illustrated by the following examples.

EXAMPLE 1. 0.5 g of phenylindane (2.1 mmol) dissolved in 3.5 ml of dichlorobenzene, 0.85 ml (12.71 mmol) of 67% nitric acid, 0.16 g of catalyst (amorphous mesoporous) are charged into a glass heated reactor with a stirrer, reflux condenser and thermometer. aluminosilicate). The reaction is carried out with constant stirring at a temperature of 110 ° C for 8 hours. The reaction mass is filtered off from the catalyst, unreacted phenylindane and mononitrophenylindanes are isolated by vacuum distillation. Dinitrophenylindanes are isolated by recrystallization from CCl ₄ . 0.47 g of product is obtained. The phenylindane conversion is 100 mol%, the selectivity for 5 (6) nitro-1- (4-nitrophenyl) -1,3,3-trimethylindane is 66 mol%.

EXAMPLES 2-10 Analogously to example 1. The conditions and results of the examples are presented in the table.

The reaction time is 8 hours

Claims (1)

The method of obtaining 5- and 6-nitro-1- (4-nitrophenyl) -1,3,3-trimethylindanes by the interaction of 1,1,3-trimethyl-3-phenylindane with nitric acid, characterized in that the nitration of 1,1,3 -trimethyl-3-phenylindane is carried out in the presence of a catalyst - amorphous mesoporous aluminosilicate - at 100-130 ° C with a molar ratio of phenylindane: HNO ₃ = 1: 6 ÷ 14 for 8 hours in the presence of 2-4 wt.% (calculated on reaction mixture) of a catalyst.

Images