CS198707B1 - 5-nitro-2-furyl-vinylene azide and method for preparing the same - Google Patents

Description

The present invention relates to 5-nitro-2-furylvinylene azide and to a process for its preparation.

5-Nitro-2-furylvinylene azide has not been prepared in the literature.

The process according to the invention is characterized in that 5-nitro-2-furylvinylene bromide is treated with sodium azide reep. potassium in solvents such as water, aromatic liquid hydrocarbons, ketones such as acetone, methyl ethyl ketone, dimethylformamide, dimethylsulfoxide, ethyl acetate, tetrahydrofuran, dioxane, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride or mixtures thereof 55 ° H.

The reaction proceeds according to Bohémyt

where M is Na, K

The second method of the present invention consists in treating 5-nitro-2-furylvinylene trimethylammonium bromide with sodium azide and sodium azide, respectively. potassium in a solvent such as water, aromatic liquid hydrocarbons, dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, alcohols, aromatic and aliphatic halogenated hydrocarbons such as chlorobenzene, dichloromethane, chloroform, carbon tetrachloride or mixtures thereof, or acetonitrile; temperature - 5 to + 55 ° C.

198 707

Reakoia runs according to Bohema:

OH-CH-N / CH ₃ / Br ₃ + ₃ * of the MN.

CH = CH-N + M ₃ / CH _3/3-MBT wherein M is Na, E

An advantage of the process according to the invention for the preparation of 5-nitro-2-furylvinylene azide is, inter alia, that the synthesis is one-step from relatively available raw materials, the products obtained are in high yields (60-82% in the first case, 80-95% in the second case) and high purity.

Example. 1

2.18 g (0.01 mol) of 5-nitro-2-furylvinylene bromide (Z isomer) in 45 ml of acetone is mixed with β 0.7 g of NaN ₃ in 5 ml of water. After stirring at room temperature for 5 hours in the absence of light, acetone was distilled off in vacuo and the residue was extracted by adding 10 ml of water to 100 ml of ether. The ether layer aa was washed twice with 10 ml of water each time and dried with MgSO 4. After distilling off the solvent, the residue was purified by column chromatography (silica gel 150-250 mesh, eluent benzene, chloroform, ether). 1.35 g (75%) of 5-nitro-2-furylvinylene azole of mp 62-65 ° C are obtained. Z and B isomer 2: 3 (according to ¹ H NMR data).

Example 2

2.18 g (0.01 mal) of 5-nitro-2-furylvinylene bromide (Z and E isomer) in 50 ml of DMF are mixed with 0.8 g of KN ₃ in 10 ml of water. After stirring at 30-40 ° C for 5 hours, the solution was poured into water. The organic material was extracted into ether. The ether layer was separated and dried to give MgSO4. After distilling off the solvent, the residue is purified by chromatography on a column (silica gel 150-250 mesh, eluent benzene, chloroform, ether). 1.08 g (60%) of 5-nitro-2-furylvinylene azide, mp 69-74 ° C, is obtained. Z and E isomer in 2: 5 ratio.

Example 3

To a solution of 2.77 g (0.01 mole) of 5-nitro-2-furylvinylene trimethylammonium bromide in 50 ml of HgO and a solution of 1 g of NaN ₃ in 15 ml of HgO is added. Reakoia proceeds immediately with the exclusion of yellow crystalline 5-nitro-2-furylvinylene azide. 1.66 g (92%) of mp 84-86 ° C / crystal are obtained. ether /.

Example 4

To a solution of 5.44 g (0.02 mol) of 5-nitro-2-furylvinylene trimethylammonium bromide in 50 ml of water and a solution of 2.5 g of sodium azide in 50 ml of water and 100 ml of ether was added. The reaction proceeds gradually with intense coloring of the ether layer. The ether layer was separated and successively poured into ether (2 x 100 mL). After separation of the combined ether fractions and drying with MgSO4 and removal of the solvent by distillation, 3.24 g, i. 90% 5-nitro-2-furylvinylene azide, m.p. 84-86 ° 0th

The 5-nitro-2-furylvinylene azide of the invention is a compound of formula

The general formula of the compound is C 8 H 11 H 2 O 3. The molecular weight is 180.12 and the melting point for the Z isomer is 62-64 ° C and for the E isomer is 83-86 ° C.

Elemental analysis:

% C % N calculated 40,01 2.24 31.11 Find them 39,83 2.18 30.98

The structure of the 5-nitro-2-furylvinylene azide according to the invention was proved by spectral methods namely IR, UV, ¹ H, NMR spectroscopy and mass spectroscopy.

UV spectra were measured on a spectrophotometer! / UV VIS fy. Zeiss Jena. Methanol was used as solvent. The compound exhibits an absorption band at:

E isomer Λ = 393 nm / log ¢. = 4.03 // _max

Z isomers _max “378 nm / logg» 3.89 /

IR spectra were measured on a spectrophotometer (UR-20- from Zeiss, Jena) in OHCl 2. The episode * trum shows the following characteristic bands:

/ ν0 ₂ ^{132 °} » ^{1530 om} @ -1 = ^{1642 om} * ^N 3 2135 om @ 1 H NMR spectrum was measured on a spectrophotometer (BS-487C from Tesla Brno).

1 H NMR spectrum was obtained by measuring the substance in CDCl 3 using tetramethylsilane as an internal standard

H, ₂ n-

, -ch _a = ch _b - n ₃ ^J 4 ^H 3

Z isomer doublet 6.89 ppm doublet 7.31 ppm doublet 6.65 ppm doublet 5.70 ppm ^J 3.4 -4Hz

J _AB «8Hz

E isomer doublet 6.35 ppm doublet 7.30 ppm doublet 7.13 ppm doublet 6.07 ppm ^J 3.4 " ^{4 Hz}

J, -13.6 Hz

The mass spectrum was measured on a spectrophotometer (MS902S of AEI).

Characteristic fragments m m / ej; 180, 152, 139, 123, 112, 106, 79, 68, 52.

The compound of the invention 5-nitro-2-furylvinylene bromide exhibits high biological activity against both O- and G ⁺ bacteria. The antibacterial effect was monitored using a diffusion plate method with adjustments required for individual microorganisms to selected bacterial yeast and fungal strains.

0 ⁺ MIC Staphylococous pyogenes in g / per disk 50 Staphylooooous faeoalis 200 Baoillus subtilis 12.5 cT Proteus vulgaris 200 Esoherichis ooli 50 MIC  minimal inhibitory condensation The 5-nitro-2-furylvinylene azide of the invention is a compound

The synthesis of compounds with a wide variety of synthetic uses as a key intermediate for the synthesis of novel compounds.

Claims (3)

OBJECT OF THE INVENTION 1. 5-Nitro-2-furylvinylene azide, model I / 1 / 2. A process for the preparation of 5-nitro-2-furylvinylene azide according to item 1, characterized in that for 5-nitro-2-furylvinylene bromide of the formula II: CH - CH - Br (11) is treated with sodium azide and resp. potassium in a solvent such as water, aromatic liquid hydrocarbons, ketones such as acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, ethyl acetate, tatrahydrofuran, dioxane, halogenated hydrocarbons such as di-chloromethane, chloroform, carbon tetrachloride or ioh + 55 ° C . 3. A process for the preparation of 5-nitro-2-furylvinylene azide according to claim 1, characterized in that for 5-nitro-2-furylvinylene trimethylammonium bromide of formula III CH-N © / CH _3/3 Bi® / 111 / is treated with sodium azide respectively. potassium in a solvent environment such as water, aromatic liquid hydrocarbons, dimethylformamide, dimethylsulfoxide, dioxene, tetrehydrofuran, N-methyl-2-pyrrolidone, C 1 -C 4 alcohols, aromatic and aliphatic halogenated hydrocarbons such as diohalomethane, halobenzene, chloroform, acetonitrile, carbon tetrachloride The temperature ranges from -5 to + 55 ° C.