2-phenyl-1,2,3-triazole production method

FIELD: chemistry.

SUBSTANCE: new production method of 2-phenyl-1,2,3-triazole using glyoxal phenylosazone ring formation with new triflate copper catalyst Cu(OSO2CF3)2, both without solvent in melt at 130°C and in high-boiling solvent mediums (toluene, o-xylene, butanol) at boiling temperatures. End product is extracted with high yield column chromatography.

EFFECT: development of new production method of 2-phenyl-1,2,3-triazole.

3 cl, 5 ex

 

The invention relates to the field of high-energy compounds, in particular to a method for producing 2-phenyl-1,2,3-triazole, which is a promising precursor for the synthesis of energy-active materials, namely, 4-nitro-1,2,3-triazole.

Known methods for producing 2-phenyl-1,2,3-triazole by dry distillation of phenylacetone glyoxal [H.V.Pechmann. Annalen der Chemie. 1891. W. S.265-277] (yield 20%); when heated to 75-100°phenylacetone glyoxal with a water solution of copper sulphate (CuSO4) for 6.5 h, followed by separation of the product by steam distillation and the respective treatment [J.L.Riebsomer. J. Org. Chem. 1948. V.13. No. 6. P.815-821; El-Khadem, H., El-Shafei Z.M. J. Chem. Soc. 1958. No. 9. P.3117-3119] (exit 59 and 50%, respectively); when heated to 180-210°phenylacetone glyoxal with a catalytic amount of odnoklasniki copper (CuCl) [Uhananov. In kN. Methods of obtaining chemicals and drugs. M.: Chemistry. 1969. VIP. S-198] (output 66.6%). The disadvantages of the above methods to obtain 2-phenyl-1,2,3-triazole are low output, high reaction temperature, and the use of water vapor (in the case of low temperature reactions).

Closest to the claimed invention (prototype) is a method of synthesis of 2-phenyl-1,2,3-triazole by cyclization of phenylacetone glyoxal under the action of catalyst CuCl in the presence of anhydrous CaCl2in races the lava at 170-190° With, the whole process includes 9 stages: 1) - synthesis, i.e. cyclization of phenylacetone glyoxal, followed by distillation of the product from the reaction mixture, with 2-phenyl-1,2,3-triazole Argonauts with aniline in the range: 170°/45-50 mm Hg - 190°C/10 mm RT. Art.; 2) processing whisked mixture of water, mixing and acidification with 20% sulfuric acid; 3) separation of the organic layer (the first fraction of 2-phenyl-1,2,3-triazole) in a separating funnel; 4) - saturation obtained aqueous solution of sodium chloride; 5) extraction of 2-phenyl-1,2,3-triazole with ether (2 times) and combining it with the first fraction; 6) drying of the combined extracts with anhydrous sodium sulfate; 7) Department of the solution of 2-phenyl-1,2,3-triazole from the dehydrator (filter); 8) removing the solvent (ether); 9) the selection of the target product (2-phenyl-1,2,3-triazole) by distillation in vacuum [Lioresal, Wmiquery, Viederman, Gagarian, Lperrno, Vimruntime. Zhur.org.chem.. 1989. V.25. VIP. S-1747] (yield 75%).

The disadvantage of the above prototype is based on complexity (multi-stage) process of selection of the target product, as well as the high temperature of receipt.

The purpose of our invention is to simplify the method of obtaining 2-phenyl-1,2,3-triazole.

This goal is achieved:

1) the use of a fundamentally new catalyst - triflate copper Cu(OSO2 CF3)2for cyclization of phenylacetone glyoxal, which, as in the prototype, is the starting reagent for the synthesis; the use of a new catalyst can reduce the process temperature to 130°if the process is conducted without solvent;

2) using high-boiling solvents (toluene, o-xylene, butanol) at temperatures of their boiling (110-145°C), which also reduces the temperature of the process, and it should be noted that prior to this, none of the known methods solvents were not used;

3) using the method of column chromatography for separation of 2-phenyl-1,2,3-triazole (silicagel LSL2545/40 μ, eluent: hexane: sulphuric ether in the ratio 1:2), which greatly simplifies the process of selection, allowing you to reduce the total number of stages to three in the case of fusion without solvents and up to four, when the process is conducted in solvents (see examples).

It should be noted that the results obtained by the proposed method 2-phenyl-1,2,3-triazole, characterized by a high degree of purity: 99.96-100%according to gas chromatography-mass spectrometry. Scheme of synthesis of 2-phenyl-1,2,3-triazole can be represented as follows:

The following neogranichivatsya examples illustrate the invention.

Cyclization vinilos the area of glyoxal in the melt

Example 1. Selection 2-phenyl-1,2,3-triazole without column chromatography. In the flask vyurts placed well mixed mixture of phenylacetone glyoxal 1 g (4.2 mmol) and triflate copper Cu(OSO2CF3)20.05 g (0.14 mmol). The reaction mixture was heated in a stream of argon to 130°With (until complete melting of osazone glyoxal) with subsequent distillation of the distillate (2-phenyl-1,2,3-triazole-aniline) at 130°s/90 mm Hg - 105°/17 mm Hg Total process time 50 min, including the time of melting of the source phenylethanone glyoxal, the process of cyclization and distillation of the distillate. Next was in the process of selection of the target product in the resulting distillate was added sulphuric ether; the ether solution was treated with 10% hydrochloric acid in a separating funnel to remove aniline, washed with distilled water until a negative reaction to chlorine ion, dried over calcined potassium carbonate. After distillation of the ether substance was distilled in a vacuum. Received 0.5 g (82.0%, the yield is higher than that of the prototype) 2-phenyl-1,2,3-triazole, colorless liquid, so Kip. 96°C/10 mm Hg, nd20=1.5880. Rf=0.84. Monitoring the progress of reactions was carried out using thin layer chromatography, using a plate with a fixed layer "Silufol", eluent: hexane-sulfuric ether (1:2), and gas chromatography-mass spectrometry. (Mass spectra were obtained on chromatography-mass-SP is chromate GCMS-QP5050A, the Shimadzu). Found, %: C at 66.23, H 5.09, N 28.55. Calculated for C8H7N3, %: 66.21, H 4.82, N 28.97. Product purity 99.96% (according to gas chromatography-mass spectrometry). The IR spectrum (νcm-1) 2-phenyl-1,2,3-triazole are all characteristic bands of stretching vibrations of relations With Mr. triazole cycle when 3139 ate. and 3124 SL., benzene ring at 3080 SL., 3059 SL., 3036 SL., C=C aromatic ring in 1599 S., 1502 O.S, 1476 SL., non-planar deformation vibrations of CH monosubstituted benzene ring at 755 and 694, valence fluctuations triazole cycle at 1410 S., S. 1376, deformation vibrations of C-C and C-H linkages triazole cycle at 1260 C., 1103 SL., 1086 cf., 1022 cf., 961 S., 951 S., 912 cf., 822 S., 669 S. (IR-spectra were recorded on a spectrometer Bruker IFS-25 in the microlayer). NMR1H (δ, ppm): 8.03, 7.55, 7.41 (resonance signals of protons of the phenyl fragment), 8.11 (resonance signal of a proton triazole fragment in position 4,5 2-phenyl-1,2,3-triazole is manifested). NMR13With (δ, ppm): 139.31 (ipso), 129.73 (meta), 127.75 (pair) and at 118.50 (ortho) (resonance signals of the carbon atoms of the phenyl ring); 136.47 (resonance signal-4,5 triazole fragment). (The NMR spectra of1H and13Filmed on device "Bruker", model DPX 400 (400 MHz) in DMSO-d6).

Example 2. Selection 2-phenyl-1,2,3-triazole using column chromatography.

In the flask vyurts put mashed and well PE is Emesene a mixture of 2 g (8.4 mmol) of phenylacetone glyoxal and triflate copper Cu(OSO 2CF3)20.1 g (0.28 mmol). Synthesis of 2-phenyl-1,2,3-triazole was carried out similarly to example 1 to highlight the distillate. And then the separation of 2-phenyl-1,2,3-triazole from aniline was carried out on column height 46 cm, diameter 2 cm, filled with silica gel (brand LSL2545/40 μ) - the ratio of the purified mixture of substances to the sorbent is 1:50. Eluent: hexane-sulfuric ether (1:2). Under this allocation method, the number of process steps is reduced to three compared with the prototype: 1) the synthesis: the cyclization of phenylacetone glyoxal; 2) the filtration from the solid catalyst particles; 3) selection 2-phenyl-1,2,3-triazole by the method of column chromatography. Got 0.98 g (80.7%, the yield is higher than in the prototype) 2-phenyl-1,2,3-triazole, so Kip. 96°C/10 mm Hg, nd20=1.5880. The purity of the product 100%.

Cyclization of phenylacetone glyoxal in solvents

Example 3. In a three-neck flask equipped with a stirrer, a refrigerator, a pipe for input of argon was placed well mixed mixture fenlason glyoxal 1 g (4.2 mmol) and triflate copper Cu(OSO2CF3)20.05 g (0.14 mmol) and 10 ml of toluene. The reaction mixture was heated at 110°C. the reaction Time is 7 o'clock monitoring the progress of reactions was carried out using thin layer chromatography, using a plate with a fixed layer "Silufol", eluent: hexane-sulfuric ether (1:2), and gas chromatography-mass spectrometry. is the ass end cyclization toluene was distilled on a water-jet pump. Selection 2-phenyl-1,2,3-triazole were performed on a column filled with silica gel (brand LSL2545/40 μ), eluent: sulfuric ether-hexane (2:1). The process proceeds in four stages: 1) the synthesis: the cyclization of phenylacetone glyoxal; 2) the filtration from the solid catalyst particles; 3) the distillation of the solvent; 4) allocation of 2-phenyl-1,2,3-triazole by the method of column chromatography. Received 0.55 g (90.2%) of 2-phenyl-1,2,3-triazole, so Kip. 94°/8 mm Hg, nd20=1.5880. The purity of the product is 100% according to gas chromatography-mass spectrometry.

Example 4. In conditions similar to those specified in example 3, was placed well mixed mixture fenlason glyoxal, 2 g (8.4 mmol) and triflate copper Cu(OSO2CF3)20.1 g (0.28 mmol) and 20 ml of o-xylene. The reaction mixture was heated at 145°C. the reaction Time of 6.5 hours monitoring the progress of reactions was carried out using thin layer chromatography, using a plate with a fixed layer "Silufol", eluent: hexane-sulfuric ether (1:2), and gas chromatography-mass spectrometry. After cyclization of the reaction mixture was filtered, the catalyst, o-xylene was distilled at rotatethe. Selection 2-phenyl-1,2,3-triazole was carried out similarly to example 3. Got 0,98 g (74.0%) of 2-phenyl-1,2,3-triazole, BP. 96°C/10 mm Hg, nd20=1.5880. Product purity 99.98% according to gas chromatography-mass spectrometry.

Example 5. In the conditions, and the illogical specified in example 3, placed well mixed mixture of phenylacetone glyoxal 1 g (4.2 mmol) and triflate copper Cu(OSO2CF3)20.05 g (0.14 mmol) and 10 ml n-butanol. The reaction mixture was heated at 117°C. the reaction Time is 7.5 hours After cyclization of the reaction mass was filtered, the catalyst, the butanol was distilled at rotatethe. Selection 2-phenyl-1,2,3-triazole was carried out similarly to example 3. Yield 0.47 g (68.0%) of 2-phenyl-1,2,3-triazole, BP. 94°/8 mm Hg, nd20=1.5880. Product purity 99.98% according to gas chromatography-mass spectrometry.

1. The method of obtaining 2-phenyl-1,2,3-triazole by cyclization of phenylacetone glyoxal, when heated in the presence of a copper salt as a catalyst, followed by separation of the target product, characterized in that as a salt of copper use triplet copper and the process is carried out without solvent at 130°C for 50 min, and the high-boiling solvents at temperatures of their boiling within the 6.5 to 7.5 h, and to highlight 2-phenyl-1,2,3-triazole using the method of column chromatography.

2. The method according to claim 1, characterized in that as high-boiling solvents used toluene, o-xylene, butanol.

3. The method according to claim 1, characterized in that for column chromatography as a stationary phase using silicagel LSL2545/40 μand as eluent a mixture of hexane:sulphuric ether in the ratio 1:2.



 

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