Method for synthesis of 2,5,8-triazido-sim-heptazine

FIELD: chemistry.

SUBSTANCE: described is an improved method for synthesis of 2,5,8-triazido-sim-heptazine of formula (I) by reacting 2,5,8-trichloro-sim-heptazine with an azidation agent in form of sodium azide in the medium of aqueous acetone at room temperature, followed by extraction of the end product via deposition from water. The invention can be used in organic synthesis.

EFFECT: high-tech and cheap method for synthesis of 2,5,8-triazido-sim-heptazine of formula (I) from commercially available 2,5,8-trichloro-sim-heptazine and a cheap azidation agent in simpler conditions for synthesis and extraction of the end product with high output and purity.

 

The invention relates to a method for 2,5,8-triazido-SIM heptadine formula (I).

2,5,8-Triazido-SIM gaptain (I) is predstaviteley energy-intensive polysomnogram organic compounds used to obtain a variety of carbide-nitride nanomaterials: nanoclusters, nanolayers, nanospheres and nanotubes (See, H.Gao, J.A.Boatz et al., Angew. Chem. Int. Ed., 2006, 45, 7262; M.H.V.Huynh, M.A.Hiskey, D.E.Chavez et al., J. Amer. Chem. Soc., 2005, 127, 12537). These carbide-nitride nanomaterials have a high mechanical strength, are chemically inert and biocompatible, which is of great interest for their use as coatings in the manufacture of implants for medicine cabinets and anodes of lithium batteries, variety of parts for the chemical industry and aerospace technology (M.H.V.Huynh, M.A.Hiskey, J.G.Archuleta et al., Angew. Chem. Int. Ed., 2005, 44, 737). Obtaining carbide-nitride nanomaterials by thermal decomposition of triazide (I) is described in the literature (D.R.Miller, J.R.Hoist, E.G.Gillan, Inorg. Chem., 2007, 46, 2767).

A method of obtaining polyethylsiloxane derivatives SIM-triazine (M.H.V.Huynh, M.A.Hiskey, E.L.Harthne et al., Angew. Chem. Int. Ed., 2004, 43, 4924), which is the closest analogues of the compound (I), according to which the introduction of sidegroup in the triazine ring is carried out by nucleophilic substitution of chlorine atoms guide what asinam and subsequent diazotization-sideropenia intermediate obtained polimerisation triazines. The disadvantage of this method of production is the technological complexity of the stage of diazotization-sideropenia of polyhydrazides, which is explosive, is in a narrow range of low temperatures (-5 - 0°C) and allows you to get targeted Polizei only low yield (<50%). In addition, this method of obtaining polyaigos requires the use of expensive hydrazine hydrate is added.

The closest technological essence and the achieved effect is described a method (D.R.Miller, D..Swenson, E.G.Gillan, J. Amer. Chem. Soc., 2004, 126, 5372) obtain triazide (I), proposed as a prototype. This method involves long-term (12 h) heating source 2,5,8-trichloro-SIM heptadine with pyatidesyatiletny molar excess trimethylsilane in nitrogen atmosphere, subsequent vacuum distillation of the volatile components of the reaction mixture and the long-term extraction of dry acetone, the solid residue to conventional Soxhlet extractions.

The disadvantage of the proposed method get is used as aidarous reagent is very expensive trimethylsilylmethyl, as well as the technological complexity of the selection of the target product extraction to conventional Soxhlet extractions.

The present invention is to develop high-tech and cheap way of getting 2,5,8-triazido-SIM heptadine formula (I) and the commercially available 2,5,8-trichloro-SIM heptadine, based on the use of cheap aidarous agent and substantially more simple conditions of synthesis and selection of the target product.

The problem is solved by the claimed method of obtaining 2,5,8-triazido-SIM heptadine by interaction 2,5,8-trichloro-SIM heptadine with aidarous agent, followed by separation of the target product, where as aidarous agent take sodium azide, the process is carried out in aqueous acetone in air at room temperature, the target product are planting out of the water.

The invention is characterized by the following. Take sodium azide as aidarous agent 2,5,8-trichloro-SIM heptadine, change the environment and temperature of reaction. Instead prolonged boiling of trichloride in solution trimethylsilane at 100°C in an atmosphere of nitrogen source trichloride stirred with an excess of sodium azide in aqueous acetone at room temperature in air. The process of selection of the target product is simplified, instead of vacuum distillation of the excess trimethylsilane and subsequent extraction with dry acetone, the solid residue to conventional Soxhlet extractions of water-insoluble target product are planted out of the water.

To obtain the target product are encouraged to use the molar ratio of the original 2,5,8-trichloro-SIM heptadine and azide on the rija from 1/3 to 1/10, because when the ratio is less than 1/3 the reaction does not take place before the end, and when the reagent ratio of more than 1/10 of their consumption is not rational. The process is conducted at a volumetric ratio of water to the acetone from 1/100 to 1/10, with less regard to the water content of the reaction rate is low, but elevated ratio is the separation of organic and aqueous phase, the reaction slows down. The synthesis of the target product is carried out in the temperature interval from 15 to 70°C. the time of reaction is not less than 0.5 hours, mostly one hour.

The invention is characterized by the following examples.

Example 1. To a solution of 2.75 g (10 mmol) 2,5,8-trichloro-SIM heptadine in 200 ml of acetone was added dropwise a solution of 2.60 g (40 mmol) of sodium azide in 20 ml of water and the resulting mixture was stirred at room temperature for 1 h, after which the acetone drove under reduced pressure and to the residue was added 150 ml of distilled water. The precipitation was filtered, washed on the filter with 100 ml of water, dried in the dark in air and recrystallized from acetone. Received 2,5,8-triazido-SIM gaptain (I) with so different. 185°C in the form of light yellow crystals. The weight of 2.78 g (94%). Found (%): 24,52, N 75,48; C6N16; Calculated (%):24,33, N 75,67. IR-spectrum (microcrystalline film, ν, cm-1): 2196, 2155, 2141 and 2115 (N3), 1605, 1558, 1540, 1339, 1206, 803. An NMR spectrum13(100,6 MHz, CDCl3, δ, ppm): 15,8 (C=N), which is 171,5 (C-N3).

Example 2. To a solution of 2.75 g (10 mmol) 2,5,8-trichloro-SIM heptadine in 200 ml of acetone was added dropwise a solution of 1.95 g (30 mmol) of sodium azide in 15 ml of water and the resulting mixture was stirred at room temperature for 0.5 h, after which the acetone drove under reduced pressure and to the residue was added 200 ml of distilled water. The precipitation was filtered, washed on the filter with 200 ml of water, dried in the dark in air and recrystallized from acetone. Received 2,5,8-triazido-SIM gaptain (I) with so different. 185°C in the form of light yellow crystals. The weight of 2.66 g (90%). Found (%): 24,47, N 75,53; C6N16; Calculated (%):24,33, N 75,67.

Example 3. To a solution of 2.75 g (10 mmol) 2,5,8-trichloro-SIM heptadine in 200 ml of acetone was added dropwise a solution of 3.90 g (60 mmol) of sodium azide in 20 ml of water and the resulting mixture was stirred at room temperature for 45 min, after which the acetone drove under reduced pressure and to the residue was added 200 ml of distilled water. The precipitation was filtered, washed on the filter with 200 ml of water, dried in the dark in air and recrystallized from acetone. Received 2,5,8-triazido-SIM gaptain (I) with so different. 185°C in the form of light yellow crystals. The weight of 2.97 g (95%). Found (%): 24,44, N 75,56; C6N16; Calculated (%):24,33, N 75,67.

Thus, we offer a new way to get 2,5,8-triazido-SIM-heptane is a (I) from commercially available 2,5,8-trichloro-SIM heptadine solves all the tasks, and it is significantly easier and cheaper way to obtain the target product and at the same time maintains its high output. According to the IR spectroscopy polecamy new way 2,5,8-triazido-SIM gaptain superior to the purity of the product obtained by the former method, in the IR spectrum which was attended by the absorption band of the original trichloride (D.R.Miller, D..Swenson, E.G.Gillan, J, Amer. Chem. Soc., 2004, 126, 5372).

The method of obtaining 2,5,8-triazido-SIM heptadine by interaction 2,5,8-trichloro-SIM heptadine with aidarous agent, followed by separation of the target product, characterized in that as aidarous agent take sodium azide, the process is carried out in aqueous acetone in air at room temperature, and the target product are planting out of the water.



 

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